JP2005264135A - Organic and inorganic complex composition, plastic base plate, gas barrier laminated film, and image display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas barrier laminated film with excellent durability, heat resistance, gas barrier property even under bending condition and small difference in coefficient of linear expansion with a neighboring layer. <P>SOLUTION: The gas barrier laminated film is prepared by forming at least one pair of inorganic and organic layers on the base film containing an inorganic compound formed with a resin having a glass transition temperature of 250°C or higher. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a gas barrier laminate film having excellent gas barrier properties and an image display element using the film. In particular, the present invention relates to a gas barrier laminate film used as a substrate for a flexible organic electroluminescence element (hereinafter referred to as “organic EL element”) and an organic EL element using the film. The present invention also relates to a novel organic / inorganic composite composition, and further relates to a plastic substrate useful for an image display device.

  Conventionally, a gas barrier film in which a metal oxide thin film such as aluminum oxide, magnesium oxide, silicon oxide or the like is formed on the surface of a plastic substrate or film is used to wrap an article that needs to block various gases such as water vapor and oxygen, Widely used in packaging applications to prevent the deterioration of food, industrial products and pharmaceuticals. Moreover, it is used with a liquid crystal display element, a solar cell, an electroluminescence (EL) substrate, etc. besides the packaging use. In particular, transparent substrates that have been applied to liquid crystal display elements, EL elements, etc., in recent years, have a long-term reliability and a high degree of freedom in addition to demands for lighter and larger sizes, and curved display. In addition to the high demands such as being possible, film base materials such as transparent plastics have begun to be used in place of glass substrates that are heavy, fragile and difficult to enlarge.

  In addition, the plastic film not only meets the above requirements, but also can be rolled to roll, so it is more advantageous than glass because of higher productivity and cost reduction. However, a film substrate such as a transparent plastic has a problem that the gas barrier property is inferior to glass. If a base material with inferior gas barrier properties is used, water vapor or air will permeate, causing deterioration of the liquid crystal in the liquid crystal cell, for example, resulting in display defects and deterioration of display quality. In order to solve such a problem, a gas barrier film base material in which a metal oxide thin film is formed on a film substrate has been developed.

Gas barrier films used for packaging materials and liquid crystal display elements are known in which silicon oxide is vapor-deposited on a plastic film (see Patent Document 1) and in which aluminum oxide is vapor-deposited (see Patent Document 2). Both have a water vapor barrier property of about 1 g / m ² · day. However, with the recent development of large liquid crystal displays, high-definition displays, etc., the gas barrier performance to the film substrate is required to be about 0.1 g / m ² · day in terms of water vapor transmission rate.

Recently, organic EL displays and high-definition color liquid crystal displays that require further gas barrier properties have been developed, maintaining transparency that can be used for them, and having a high barrier property, in particular, a water vapor transmission rate of 0.1 g. Substrates with performance of less than / m ² · day are required. In order to meet this demand, a sputtering method in which a thin film is formed using plasma generated by glow discharge under a low pressure condition and a film forming method by a CVD method have been studied as means for expecting higher barrier performance. In addition, a technique for producing a barrier film having an alternately laminated structure of organic layers / inorganic layers by a vacuum deposition method has been proposed (see Patent Document 3 and Patent Document 4).

  However, for use as a flexible organic EL display substrate, the gas barrier films described in Patent Documents 3 and 4 have insufficient gas barrier properties and flex resistance, and further improvements have been desired. In addition, the polymer layer formed by the methods of Patent Documents 3 and 4 has insufficient heat resistance due to a difference in linear expansion coefficient from an adjacent layer required when the TFT of the active matrix image element is installed. Improvement was needed. Further, since the adhesion between the polymer layer and the inorganic layer was insufficient, an improvement was also required in this respect.

On the other hand, in recent years, an organic / inorganic composite composition in which a resin as an organic polymer and a metal oxide as an inorganic material are compatible has attracted attention as a material that complements the characteristics of the organic material and the inorganic material and takes advantage of the advantages. Research and development on organic / inorganic composite compositions has been actively conducted. For example, an attempt has been made to apply an organic / inorganic composite composition based on a hydrolysis condensate of an epoxy resin and an alkoxysilane having a glycidyl group to a substrate for an image display element (for example, see Patent Document 5). However, the organic / inorganic composite composition has a drawback that it is insufficient in flexibility and is brittle. On the other hand, an organic / inorganic composite composition using polycarbonate and an inorganic material as a more flexible thermoplastic resin is also known (see, for example, Patent Document 6). However, the polycarbonate used here has insufficient heat resistance.
Japanese Examined Patent Publication No. 53-12953 (pages 1 to 3) JP 58-217344 A (pages 1 to 4) US Pat. No. 6,268,695 (4th page [2-5] to 5th page [4-49]) JP 2003-53881 A (page 3 [0006] to page 4 [0008] JP-A-10-54979 (all pages) International Publication No. WO99 / 14274 (all pages)

The present invention has been made in view of the above problems, and a first object of the present invention is to provide a composition and a plastic substrate that realize an image display element substrate having excellent optical properties and display quality, Furthermore, it is providing the image display element using the same. In particular, a plastic substrate excellent in mechanical properties and an image display element using the same without being deteriorated in conductivity even when a heat treatment, an alignment film, a gas barrier film, or the like is applied after the transparent conductive film is formed. It is to provide.
The second object of the present invention is a gas barrier laminate that has excellent durability, heat resistance, and gas barrier performance, has a small difference in linear expansion coefficient from an adjacent layer, and can maintain excellent gas barrier properties even when bent. An object of the present invention is to provide a film and an image display element excellent in durability using the film.

  The present inventors have both good gas barrier properties and heat resistance, show good definition and durability when used as a liquid crystal display substrate or an organic EL substrate, and have a difference in coefficient of linear expansion from the adjacent layer. The development of a small gas barrier laminate film was studied earnestly. As a result, it has been found that the above-mentioned problems can be solved by using a base film made of a predetermined resin and an inorganic compound, and the present invention has been completed.

［一般式（Ｉ）中、環αは単環式または多環式の環を表し、２つの環はスピロ結合により結合されている。］

［一般式（II）中、環βおよび環γは、単環式または多環式の環を表し、２つの環γはそれぞれ同じであっても異なっていてもよく、環β上の１つの４級炭素に連結されている。］
（３） 前記無機化合物が、ゾルゲル法による加水分解および重縮合反応により得られた金属酸化物であることを特徴とする（１）または（２）に記載の有機・無機複合体組成物。
（４） 前記無機化合物が、負の線膨張係数を有することを特徴とする（１）〜（３）のいずれか一項に記載の有機・無機複合体組成物。
（５） 前記金属酸化物を構成する金属原子が、ケイ素、ジルコニウム、アルミニウム、チタンおよびゲルマニウムからなる群より選ばれる金属原子であることを特徴とする（１）〜（４）のいずれか一項に記載の有機・無機複合体組成物。
（６） （１）〜（５）のいずれか一項に記載の有機・無機複合体組成物からなるプラスチック基板。
（７） 金属酸化物の含有率が５質量％〜７０質量％であり、厚みが４０μｍ〜２００μｍであることを特徴とする（６）に記載のプラスチック基板。
（８） 金属酸化物を含有することにより熱変形温度が２℃以上上昇していることを特徴とする（６）または（７）に記載のプラスチック基板。
（９） 金属酸化物を含有することにより熱膨張係数が２０ｐｐｍ／℃以上低下していることを特徴とする（６）〜（８）のいずれか一項に記載のプラスチック基板。
（１０） （６）〜（９）のいずれか一項に記載のプラスチック基板上に透明導電層を有することを特徴とする透明導電層付きプラスチック基板。
（１１） 無機化合物を含有する基材フィルム上に少なくとも１組の無機層および有機層を形成してなるガスバリア性積層フィルムであって、前記基材フィルムがガラス転移温度２５０℃以上の樹脂からなるフィルムであることを特徴とするガスバリア性積層フィルム。
（１２） 前記無機化合物が、ゾルゲル法による加水分解および重縮合反応により得られた金属酸化物であることを特徴とする（１１）に記載のガスバリア性積層フィルム。
（１３） 前記無機化合物が、負の線膨張係数を有することを特徴とする（１１）または（１２）に記載のガスバリア性積層フィルム。
（１４） 前記基材フィルムが、上記一般式（Ｉ）で表されるスピロ構造を有するポリマーまたは上記一般式（II）で表されるカルド構造を有するポリマーからなるフィルムである（１１）〜（１３）のいずれか一項に記載のガスバリア性積層フィルム。
（１５） 前記基材フィルムが（６）〜（１０）のいずれか一項に記載のプラスチック基板である（１１）〜（１４）のいずれか一項に記載のガスバリア性積層フィルム。
（１６） （６）〜（１０）のいずれか一項に記載のプラスチック基板、または（１１）〜（１５）のいずれか一項に記載のガスバリア性積層フィルムを基板として用いる画像表示素子。 That is, the object of the present invention is achieved by the following gas barrier laminate film, image display device, organic / inorganic composite composition, and plastic substrate.
(1) An organic / inorganic composite composition comprising an inorganic compound and a resin having a glass transition temperature of 250 ° C. or higher.
(2) The resin is a polymer having a spiro structure represented by the following general formula (I) or a polymer having a cardo structure represented by the following general formula (II) Organic / inorganic composite composition.

[In general formula (I), ring α represents a monocyclic or polycyclic ring, and the two rings are connected by a spiro bond. ]

[In general formula (II), ring β and ring γ represent a monocyclic or polycyclic ring, and two rings γ may be the same or different from each other. Linked to quaternary carbon. ]
(3) The organic / inorganic composite composition according to (1) or (2), wherein the inorganic compound is a metal oxide obtained by hydrolysis and polycondensation reaction by a sol-gel method.
(4) The organic / inorganic composite composition according to any one of (1) to (3), wherein the inorganic compound has a negative linear expansion coefficient.
(5) The metal atom constituting the metal oxide is a metal atom selected from the group consisting of silicon, zirconium, aluminum, titanium, and germanium. Any one of (1) to (4), The organic-inorganic composite composition described in 1.
(6) A plastic substrate comprising the organic / inorganic composite composition according to any one of (1) to (5).
(7) The plastic substrate according to (6), wherein the metal oxide content is 5% by mass to 70% by mass and the thickness is 40 μm to 200 μm.
(8) The plastic substrate as set forth in (6) or (7), wherein the thermal deformation temperature is increased by 2 ° C. or more by containing a metal oxide.
(9) The plastic substrate according to any one of (6) to (8), wherein the thermal expansion coefficient is reduced by 20 ppm / ° C. or more by containing a metal oxide.
(10) A plastic substrate with a transparent conductive layer, comprising a transparent conductive layer on the plastic substrate according to any one of (6) to (9).
(11) A gas barrier laminate film formed by forming at least one inorganic layer and an organic layer on a base film containing an inorganic compound, wherein the base film is made of a resin having a glass transition temperature of 250 ° C. or higher. A gas barrier laminate film, which is a film.
(12) The gas barrier laminate film according to (11), wherein the inorganic compound is a metal oxide obtained by hydrolysis and polycondensation reaction by a sol-gel method.
(13) The gas barrier laminate film according to (11) or (12), wherein the inorganic compound has a negative linear expansion coefficient.
(14) The base film is a film made of a polymer having a spiro structure represented by the general formula (I) or a polymer having a cardo structure represented by the general formula (II). The gas barrier laminate film according to any one of 13).
(15) The gas barrier laminate film according to any one of (11) to (14), wherein the base film is the plastic substrate according to any one of (6) to (10).
(16) An image display device using the plastic substrate according to any one of (6) to (10) or the gas barrier laminate film according to any one of (11) to (15) as a substrate.

The novel organic / inorganic composite composition of the present invention provides a plastic substrate and a gas barrier laminate film excellent in mechanical properties and optical properties.
The gas barrier laminate film of the present invention is formed by forming at least one or more inorganic layers and organic layers on a base film made of a resin having a glass transition temperature of 250 ° C. or higher. By having this configuration, according to the present invention, it is possible to obtain a gas barrier laminate film having both excellent durability and heat resistance, as well as high gas barrier performance and high flexibility.

  Moreover, the image display element of the present invention uses the plastic substrate or gas barrier laminate film of the present invention as a substrate. Thus, according to the present invention, it is possible to provide an image display element, particularly an organic EL element, having a flexible substrate and excellent in high definition and durability.

  The organic / inorganic composite composition, plastic substrate, gas barrier laminate film, and image display element of the present invention will be described in detail below. For convenience of explanation, the order of explanation of the present invention is performed in the order of the gas barrier laminate film of the present invention (hereinafter also referred to as “film of the present invention”), the organic / inorganic composite composition, the plastic substrate, and the image display element. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Gas barrier laminate film]
The film of the present invention is a gas barrier laminate film formed by forming at least one set of an inorganic layer and an organic layer on a base film containing an inorganic compound. Hereinafter, each member which comprises the gas barrier laminated film of this invention is demonstrated.

<Base film>
(Inorganic compounds)
The base film used in the film of the present invention contains an inorganic compound. If the inorganic compound contained in a base film is generally used as a filler for resin (filler), it can be especially used without a restriction | limiting.

  Examples of inorganic compounds include metal oxides such as alumina, zinc oxide, titanium oxide, cerium oxide, calcium oxide, magnesium oxide, and niobium oxide; metal hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide; Carbonates such as basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite; sulfates such as calcium sulfate, barium sulfate, magnesium sulfate, gypsum fiber; calcium silicate (warastonite, Zonotlite), talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, palygorskite (attapulgite), sericite, kaolin, vermiculite, smectite Glass fiber, milled glass fiber, glass beads, glass flakes, glass-based fillers such as glass balloons; silica, silicate compounds such as silica sand, and the like ferrites and the like. Other inorganic fillers include red phosphorus, carbon black (acetylene black, oil furnace black, lamp black, etc.), graphite, graphite whiskers, carbon nanotubes, fullerene, carbon fibers, metal fibers, various metal-coated fibers, titanic acid A potassium whisker, an aluminum borate whisker, etc. can be mentioned.

  The resin filler (filler) is described, for example, in Polymer ABC Handbook (edited by Polymer Society ABC Research Group, published by NTN (2001)), pages 480-490. Furthermore, it can be classified into spherical (granular), acicular (fibrous), and plate-like depending on the shape.

When the inorganic compound is spherical (granular), the average particle size is preferably 5 nm to 1 μm, more preferably 5 to 100 nm, and further preferably 5 to 50 nm.
These inorganic compound particles may be commercially available, or may be synthesized according to Chemistry of Materials, Vol. 5, page 412 (1993). As commercially available inorganic compound particles, for example, Snowtex and alumina sol sold by Nissan Chemical Industries, Ltd., fullerene (C ₆₀ , C ₇₀ ) and the like sold by Tokyo Kasei can be preferably used.

  When the inorganic compound is acicular (fibrous), it preferably has an average aspect ratio of 5 to 10,000. At that time, the diameter of the inorganic compound is preferably 0.5 to 100 nm, more preferably 0.5 to 20 nm, and still more preferably 0.5 to 5 nm. The average length (average length in the longitudinal direction) of the inorganic compound is preferably 5 to 200 nm, more preferably 10 to 100 nm, and still more preferably 10 to 50 nm. As these inorganic compounds, natural compounds may be used, or those synthesized using the method described in JP-A No. 2000-128520 may be used.

  The inorganic compound contained in the base film of the present invention may be spherical (granular), acicular (fibrous), or plate-shaped in the above classification. The inorganic compound used in the present invention is preferably a carbon nanotube, vanadium oxide, allophane or imogolite, more preferably allophane or imogolite.

  When the inorganic compound is flat, it is preferably an inorganic compound composed of a plate having an average aspect ratio of 5 to 10,000. The plate then has an average thickness of 2.5 nm or less, preferably 0.4 to 2.5 nm, more preferably 0.5 to 2 nm and a maximum thickness of 10 nm. The average length of the plate (average length in the longitudinal direction) is preferably 2 nm to 1 μm. These flat inorganic compounds may be natural ones or synthesized ones. Examples of the flat inorganic compound include layered silicates and layered oxides.

The layered silicate contained in the tabular inorganic compound is, for example, smectic clay mineral, vermiculite clay mineral, mica, montmorillonite, nontronite, beidellite, bolcon score, hectorite, stevensite, pyroloysite, saponite, sauconite, magadiite, Bentonite, Kenyaite and the like can be mentioned. As the layered oxide, K ₄ Nb ₆ O ₁₇ , H ₂ Ti ₄ O ₉ , H ₃ Sb ₃ P ₂ O _14, or the like can be used.

A commercial item may be used for the said flat inorganic compound, and what was synthesize | combined based on Revue de Chimie minerale magazine, the 23rd, 766th pages (1986), etc. may be used.
As commercially available tabular inorganic compounds, Sumecton SA from Kunimine Industries, Kunipia F from Kunimine Industries, Somasif ME-100 from Corp Chemical, Lucentite SWN from Corp Chemical, etc. can be preferably used. More preferably, it is Lucentite SWN manufactured by Corp Chemical.

  The spherical, plate-like, and tabular inorganic compounds used in the base film of the present invention are used in a state of being dispersed in the resin. Therefore, it is preferable that the surface of the inorganic compound has a structure having high affinity with the polymer. For this purpose, the surface of the inorganic compound is made organophilic by the method disclosed in US Pat. No. 2,531,365, the method disclosed in JP-A-11-43319, and the like. Preferably it is.

In the base film of the present invention, silsesquioxanes can also be preferably used as the inorganic compound. Silsesquioxane is a compound represented by [RSiO _3/2 ]. Silsesquioxane is usually synthesized by hydrolysis-polycondensation of RSiX ₃ (R = hydrogen atom, alkyl group, alkenyl group, aryl group, araalkyl group, etc., X = halogen, alkoxy group, etc.) type compound. Siloxane, which is typically an amorphous structure, ladder structure, cage structure, or partially cleaved structure (a structure in which a silicon atom is missing from a cage structure or a cage structure). A structure in which the silicon-oxygen bond is partially broken) is known. Among the above silsesquioxanes, cage silsesquioxane and its partially cleaved structure are preferably used for the base film of the present invention.

As the cage silsesquioxane, silsesquioxane of the following general formula (1) represented by the chemical formula of [RSiO _3/2 ] _{8 and} the following general formula of the chemical formula of [RSiO _3/2 ] ₁₀ (2) Silsesquioxane, [RSiO _3/2 ] ₁₂ represented by the chemical formula of the following general formula (3) Silsesquioxane, [RSiO _3/2 ] ₁₄ represented by the following general formula Examples thereof include silsesquioxane of (4) and silsesquioxane of the following general formula (5) represented by the chemical formula of [RSiO _3/2 ] ₁₆ .
The value of n in the cage silsesquioxane represented by [RSiO _3/2 ] _n is an integer of 6 to 20, preferably 8, 10 or 12, particularly preferably 8 alone or 8 A mixture of 10 and 12.

A partially cleaved structure of a cage silsesquioxane can also be preferably used as an inorganic compound contained in the base film of the present invention. A partially cleaved structure of a cage silsesquioxane is a [RSiO _3/2 ] _nm (O _1/2 H) _{2 + m in which} a part of the silicon-oxygen bond of the cage silsesquioxane is partially cleaved. (N is an integer of 6 to 20, and m is 0 or 1). Preferably, a silsesquioxane of the following general formula (6) represented by a chemical formula of trisilanol body [RSiO _3/2 ] ₇ (O _1/2 H) ₃ in which a part of the general formula (1) is cleaved, Silsesquioxane of the following general formula (7) represented by a chemical formula of [RSiO _3/2 ] ₈ (O _1/2 H) _2, a chemical formula of [RSiO _3/2 ] ₈ (O _1/2 H) ₂ It is the silsesquioxane of General formula (8) represented by these.

  In the general formulas (1) to (8), R is a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an araalkyl group having 7 to 20 carbon atoms, or It is an aryl group having 6 to 20 carbon atoms.

  Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, butyl group (n-butyl group, i-butyl group, tert-butyl group, sec -Butyl group, etc.), pentyl group (n-pentyl group, i-pentyl group, neopentyl group, cyclopentyl group etc.), hexyl group (n-hexyl group, i-hexyl group, cyclohexyl group etc.), heptyl group (n- Heptyl group, i-heptyl group, etc.), octyl group (n-octyl group, i-octyl group, tert-octyl group etc.), nonyl group (n-nonyl group, i-nonyl group etc.), decyl group (n- Decyl group, i-decyl group, etc.), undecyl group (n-undecyl group, i-undecyl group, etc.), dodecyl group (n-dodecyl group, i-dodecyl group, etc.) and the like. In consideration of the balance of melt fluidity, flame retardancy and operability during molding, it is preferably a saturated hydrocarbon having 1 to 16 carbon atoms, particularly preferably a saturated hydrocarbon having 1 to 12 carbon atoms.

  As the alkenyl group having 2 to 20 carbon atoms, both acyclic alkenyl groups and cyclic alkenyl groups can be used. Examples thereof include vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, cyclohexenyl group, cyclohexenylethyl group, norbornenylethyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, A dodecenyl group etc. are mentioned. The alkenyl group is preferably an alkenyl group having 16 or less carbon atoms, particularly preferably 12 or less carbon atoms in consideration of the balance of melt fluidity, flame retardancy and operability during molding.

  Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group, a phenethyl group, or a benzyl group, a phenethyl group, etc., which are substituted by 1 or more carbon atoms in an alkyl group having 1 to 13, preferably 1 to 8 carbon atoms. Is mentioned.

  Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, or a phenyl group, a tolyl group, and a xylyl group substituted with an alkyl group having 1 to 14, preferably 1 to 8 carbon atoms. It is done.

  As these cage polysilsesquioxanes, compounds commercially available from Aldrich, Hybrid Plastic, Chisso, Amax, etc. may be used as they are, or Journal of American Chemical Society, 111 Vol. 1741 (1989), etc. may be used.

  The base film used in the present invention can also preferably contain an inorganic compound having a negative linear expansion coefficient. That is, in the film of the present invention, by containing an inorganic compound having a negative linear expansion coefficient in the resin of the base film, thermal expansion can be suppressed as compared with the base film made of the resin alone. This means that when the film of the present invention is used as a liquid crystal display substrate or an organic EL substrate, the thermal expansion behavior is similar to that of ITO or TFT, compared with a base film made of resin alone. Thus, curling and cracking can be made difficult to occur by heating / cooling during the production of ITO or TFT. In addition, the base film in the present invention has mechanical properties (tensile strength, elastic modulus, bending strength, dimensional stability, creep characteristics, wear resistance, compared to a base film made of a resin alone. Surface hardness, etc.), heat resistance, molding processability, flame retardancy, etc. can be improved.

U.S. Patent No. 5,322,559, U.S. Patent 5,514,559 No. and the like each _{specification, ZrW 2 O 8, HfW 2} O 8, Sc 2 (WO 4) 3, BiCu 2 VO 6, Sc 2 ( MoO ₄ ) ₃ , ZrMo ₂ O ₈ , ZrV ₂ O ₇ , HfV ₂ O ₇ , HfVPO ₇ , ZrVPO _7, etc. have been reported to have a negative coefficient of linear expansion. It can be preferably used. Further, negative thermal expansion glass ceramics mainly composed of β-eucryptite, β-eucryptite solid solution, β-quartz, β-quartz solid solution described in JP-A-2001-172048, Journal of Nb ₂ O ₅ , Nb ₂ O ₅ —TiO _{2 and the} like described in Applied Physics Vol. 91, page 5051 can also be preferably used in the present invention.

  Known methods can be used to make inorganic compounds into fine particles. For example, Chapter 7 of “Particulate Design” written by Jun Koishi (published by Industrial Research Council, 1987) includes a roll rolling mill, a high speed It has been shown that inorganic fine particles can be obtained by using a pulverizer such as a rotary pulverizer, a ball mill, a medium stirring mill, and a jet mill. In the present invention, the inorganic compound having a negative linear expansion coefficient contained in the base film is desirably dispersed in the base material in a state of being finely divided by these methods.

When the inorganic compound having a negative linear expansion coefficient is an inorganic oxide, it can be synthesized as fine particles by a sol-gel reaction using a corresponding metal alkoxide as a starting material. For example, Nb ₂ O ₅ fine particles can be obtained by a sol-gel reaction using Nb (OEt) ₅ as a starting material.

  Since the inorganic compound in the present invention is used in a state of being dispersed in the resin, it is preferable to have an affinity for the polymer by performing a surface treatment. Examples of the surface treatment agent used in the present invention include a silane-based surface treatment agent, a titanate-based surface treatment agent, and an alumina-based surface treatment agent. From the viewpoint of reactivity, handleability, economic efficiency, and stability, A system surface treatment agent is preferably used.

  Preferable examples of the silane-based surface treatment agent include silane coupling agents represented by the following general formula (A).

  In general formula (A), X is a hydrolyzable group or a hydroxyl group, and when a plurality of X are present, they may be different from each other. Y is an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and examples of the substituent include an epoxy group, amino group, amide group, carboxyl group, mercapto group, hydroxyl group, and halogen atom. , At least one selected from the group consisting of an acyloxy group having 2 to 8 carbon atoms, a carboxyl group esterified with an alkyl alcohol having 1 to 22 carbon atoms, and a hydroxyl group etherified with an alkyl alcohol having 1 to 22 carbon atoms Yes, when there are a plurality of Y, they may be different from each other. n is an integer of 1 to 3.

  Examples of the hydrolyzable group X in the general formula (A) include an alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.), and an alkenyloxy group having 3 to 8 carbon atoms. (For example, isopropenoxy group, 1-ethyl-2-methylvinyloxime group, etc.), ketoxime group having 3 to 8 carbon atoms (for example, dimethyl ketoxime group, methylethyl ketoxime group, etc.), acyloxy group having 2 to 8 carbon atoms ( For example, an acetoxy group, propionoxy group, butyroyloxy group, benzoyloxime group, etc.), amino group (eg, dimethylamino group, diethylamino group, etc.), aminoxy group (eg, dimethylaminoxy group, diethylaminoxy group, etc.), amide group ( For example, N-methylacetamide group, N-ethylacetamide group, N-meth Etc. Rubenzuamido group), a halogen atom (e.g., chlorine atom, bromine atom). Among these, a C1-C4 alkoxy group and a chlorine atom are preferable from a reactive viewpoint.

  As the hydrocarbon group Y in the general formula (A), an alkyl group having 1 to 25 carbon atoms having no substituent (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group) , An octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an eicosyl group, a docosyl group, etc., an alkenyl group having 2 to 25 carbon atoms having no substituent (for example, a vinyl group, 1-propenyl, etc.) Group, 1-butenyl group, 1-hexenyl group, 2-hexenyl group, 1-octenyl group, 3-octenyl group, cyclohexenyl group, etc.), an aromatic group having 6 to 25 carbon atoms having no substituent (for example, , Phenyl group, naphthyl group, etc.), C 7-25 aralkyl group (benzyl group, phenethyl group, etc.) having no substituent, C 6-2 having no substituent Cycloalkyl groups (cyclohexyl group, cyclooctyl group, etc.), substituents (for example, epoxy groups, amino groups, carboxyl groups, mercapto groups, hydroxyl groups, halogen atoms, C2-C8 acyloxy groups, C1-C10) An alkyl group having 1 to 25 carbon atoms having a carboxyl group esterified with an alkyl alcohol or a hydroxyl group etherified with an alkyl alcohol having 1 to 10 carbon atoms (hereinafter also simply referred to as “substituent”) (for example, γ- (2-aminoethyl) aminopropyl group, γ-glycidoxypropyl group, γ-mercaptopropyl group, γ-chloropropyl group, γ-aminopropyl group, etc.) having 2 to 25 carbon atoms having a substituent Alkenyl group (for example, γ-methacryloxypropyl group, 4-methyl-4-amino-1-hexenyl group), substitution C2-C25 alkynyl group (for example, (gamma) -aminopropynyl group etc.) which has C6, C6-C25 aromatic group (for example, (gamma) -anilinopropyl group etc.) which has a substituent, C7 which has substitution -25 aralkyl group (for example, N-β- (N-vinylbenzylaminoethyl) -Y-aminopropyl group), a cycloalkyl group having 6 to 25 carbon atoms having a substituent (for example, 2- (3,4-) Epoxy cyclohexyl) ethyl group, etc.). Among them, an alkyl group having 1 to 25 carbon atoms having no substituent (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, Hexadecyl group, octadecyl group, eicosyl group, docosyl group and the like are preferable.

  X, Y, and n in the general formula (A) are as described above. Specific examples of the silane surface treatment agent such as the silane coupling treatment agent represented by the general formula (A) in combination of these are as follows. For example, Y having a polymethylene chain such as decyltrimethoxysilane and octadecyldimethylmethoxysilane, Y having a lower alkyl group such as methyltrimethoxysilane and trimethylethoxysilane, and 2-hexenyltrimethoxysilane Y having an unsaturated hydrocarbon group, Y having a side chain such as 2-ethylhexyltrimethoxysilane, Y having a phenyl group such as phenyltriethoxysilane, 3-β-naphthylpropyl Y having an aralkyl group, such as trimethoxysilane, p-vinylbenzyl trimer Y having a phenylene group such as xyloxysilane, Y having a vinyl group such as vinyltrimethoxysilane, vinyltrichlorosilane, and vinyltriacetoxysilane, Y being an ester such as γ-methacryloxypropyltrimethoxysilane Having a group, Y having an ether group such as γ-polyoxyethylenepropyltrimethoxysilane, 2-ethoxyethyltrimethoxysilane, Y having an epoxy group such as γ-glycidoxypropyltrimethoxysilane Γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane and the like in which Y has an amino group, γ-ureidopropyltri Y like ethoxysilane has carbonyl group , Y having a mercapto group such as γ-mercaptopropyltrimethoxysilane, Y having halogen such as γ-chloropropyltriethoxysilane, N, N-di (2-hydroxyethyl) amino Examples include those in which Y has a hydroxyl group, such as -3-propyltriethoxysilane.

  More preferred examples of the silane-based surface treatment agent include silane coupling agents represented by the following general formula (B).

  In general formula (B), X is a hydrolyzable group or a hydroxyl group, and when a plurality of X are present, they may be different from each other. Y is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. Examples of the substituent include an epoxy group, an amino group, an amide group, a carboxyl group, a mercapto group, a hydroxyl group, and a halogen atom. At least one selected from the group consisting of an atom, an acyloxy group having 2 to 8 carbon atoms, a carboxyl group esterified with an alkyl alcohol having 1 to 22 carbon atoms, and a group etherified with an alkyl alcohol having 1 to 22 carbon atoms And when there are a plurality of Y, they may be different from each other. More preferably, in the general formula (B), X is any one of a methoxy group, an ethoxy group, and a chlorine atom, and Y is a linear alkyl group, and most preferably any of trimethylmethoxysilane and octadecyldimethylchlorosilane. It is. These silane surface treatment agents may be used alone or in combination of two or more.

  As a method for covalently bonding the surface treatment agent to the surface of the inorganic fine particles, a known method can be used. Specifically, the surface treatment agent can be covalently bonded to the surface of the inorganic fine particles by suspending the inorganic fine particles in a solvent and then adding a surface treatment agent and reacting at room temperature or under heating conditions. Excess surface treatment agent that is not covalently bonded to the inorganic fine particles can be removed by distillation under reduced pressure or by washing with a good solvent for the surface treatment agent such as ethyl acetate, tetrahydrofuran, chloroform, or ethanol. The covalent bonding of the surface treatment agent to the inorganic fine particles can be confirmed, for example, by measuring an absorption band derived from the functional group of the surface treatment agent by infrared spectroscopy (IR).

  In the present invention, when the content of the inorganic compound contained in the base film is small with respect to the mass of the polymer, the above-mentioned effect due to the inorganic compound is often not obtained sufficiently, and the content with respect to the mass of the polymer When the amount increases, the above effect increases, but the brittleness resistance of the obtained base film tends to decrease. Therefore, the addition rate of the inorganic compound is preferably 0.1 to 50% by mass, more preferably 5 to 25% by mass with respect to the total mass of the base film (polymer + inorganic compound). More preferably, it is -20 mass%.

(Polymer used for base film)
When the base film material used in the film of the present invention is formed into a film, the inorganic layer and the organic layer can be held thereon, and the glass transition temperature (hereinafter referred to as “Tg”) is 250 ° C. or higher, preferably Is 300 ° C. or higher, more preferably 350 ° C. or higher, and any material that can be used as a barrier film substrate can be appropriately selected.
Examples of such materials include methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide resin, fluorinated polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, and cellulose acylate. Resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified polycarbonate resin, alicyclic modified polycarbonate resin, acryloyl compound And a thermoplastic resin having a Tg of 250 ° C. or higher.

  Preferred examples of the material used in the base film of the present invention include a polymer having a spiro structure represented by the following general formula (I) or a polymer having a cardo structure represented by the following general formula (II). it can. These polymers are compounds having high heat resistance, high elastic modulus, and high tensile fracture stress, and various heating operations are required in the manufacturing process, and the organic EL element is required to have a performance that is difficult to break even when bent. It is suitable as a substrate material.

  In general formula (I), ring α represents a monocyclic or polycyclic ring, and the two rings are connected by a spiro bond.

  In general formula (II), ring β and ring γ represent a monocyclic or polycyclic ring, and two rings γ may be the same or different, and one quaternary ring on ring β Linked to carbon.

  Preferred examples of the polymer having a spiro structure represented by the general formula (I) include a polymer having a spirobiindane structure represented by the following general formula (III) in the repeating unit, and a spiro represented by the following general formula (IV). Examples thereof include a polymer containing a bichroman structure in the repeating unit and a polymer containing a spirobibenzofuran structure represented by the following general formula (V) in the repeating unit.

  Moreover, as a preferable example of the polymer having a cardo structure represented by the general formula (II), a polymer having a fluorene structure represented by the following general formula (VI) in a repeating unit can be given.

In general formula (III), R ³¹ , R ³² and R ³³ each independently represents a hydrogen atom or a substituent. In addition, each may be linked to form a ring. m and n represent an integer of 1 to 3. Examples of preferred substituents are a halogen atom, an alkyl group or an aryl group. More preferred examples of R ³¹ and R ³² are hydrogen atom, methyl group or phenyl group, and more preferred examples of R ³³ are hydrogen atom, chlorine atom, bromine atom, methyl group, isopropyl group, tert-butyl group or phenyl group. It is a group.

In the general formula (IV), R ⁴¹ and R ⁴² each independently represents a hydrogen atom or a substituent. In addition, each may be linked to form a ring. m and n represent an integer of 1 to 3. Examples of preferred substituents are a halogen atom, an alkyl group or an aryl group. More preferred examples of R ⁴¹ are hydrogen atom, methyl group or phenyl group, and more preferred examples of R ⁴² are hydrogen atom, chlorine atom, bromine atom, methyl group, isopropyl group, tert-butyl group or phenyl group. is there.

In the general formula (V), R ⁵¹ and R ⁵² each independently represents a hydrogen atom or a substituent. In addition, each may be linked to form a ring. m and n represent an integer of 1 to 3. Examples of preferred substituents are a halogen atom, an alkyl group or an aryl group. More preferred examples of R ⁵¹ are hydrogen atom, methyl group or phenyl group, and more preferred examples of R ⁵² are hydrogen atom, chlorine atom, bromine atom, methyl group, isopropyl group, tert-butyl group or phenyl group. is there.

In general formula (VI), R ⁶¹ and R ⁶² each independently represents a hydrogen atom or a substituent. In addition, each may be linked to form a ring. j and k represent an integer of 1 to 4. Examples of preferred substituents are a halogen atom, an alkyl group or an aryl group. More preferred examples of R ⁶¹ and R ⁶² are a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, an isopropyl group, a tert-butyl group, or a phenyl group.

  The polymer containing the structure represented by the general formulas (III) to (VI) in the repeating unit may be a polymer linked by various bonding methods such as polycarbonate, polyester, polyamide, polyimide, polyurethane, etc. Polycarbonates, polyesters, and polyurethanes derived from bisphenol compounds having structures represented by formulas (III) to (VI) are preferred from the viewpoint of optical transparency. Among these, aromatic polyesters are particularly preferable from the viewpoint of heat resistance.

  Preferred specific examples of the polymer having a structure represented by general formula (I) and general formula (II) are shown below, but the present invention is not limited thereto.

  The polymers having the structures represented by the above general formula (I) and general formula (II) used in the present invention may be used singly or in combination. Moreover, a homopolymer may be sufficient and the copolymer which combined multiple types of structure may be sufficient. When a copolymer is used, a known repeating unit that does not contain the structure represented by the general formula (I) or (II) in the repeating unit may be copolymerized within a range that does not impair the effects of the present invention. In addition, the copolymer is more improved than the homopolymer in terms of solubility and transparency, and can be preferably used.

  The preferred molecular weight of the polymer having the structure represented by the general formula (I) and the general formula (II) used in the present invention is 1 to 500,000, more preferably 2 to 300,000, particularly preferably in terms of weight average molecular weight. 3 to 200,000. If the weight average molecular weight is 10,000 or more, a film can be easily formed and good mechanical properties can be obtained. On the other hand, if the weight average molecular weight is 500,000 or less, the molecular weight can be easily controlled in the synthesis, and an appropriate solution viscosity can be obtained, which is easy to handle. The molecular weight can be based on the corresponding viscosity.

  In the present invention, as the material used for the base film, a curable resin (crosslinked resin) excellent in solvent resistance, heat resistance and the like can be used in addition to the above polymer as long as Tg is 250 ° C. or higher. . As the curable resin, both a thermosetting resin and a radiation curable resin can be used, and those known in the art can be used without particular limitation. Examples of the thermosetting resin include phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, silicone resin, diallyl phthalate resin, furan resin, bismaleimide resin, cyanate resin and the like.

  In addition, the crosslinking method of the curable resin can be used without particular limitation as long as it is a reaction that forms a covalent bond. The reaction is performed at room temperature that forms a urethane bond using a polyalcohol compound and a polyisocyanate compound. A system in which the process proceeds can also be used without particular limitation. However, such a system often has a problem of pot life before film formation, and is usually used as a two-component mixed type in which a polyisocyanate compound is added immediately before film formation. On the other hand, when used as a one-component type, it is effective to protect the functional group involved in the crosslinking reaction, and it is also commercially available as a block type curing agent.

  As commercially available block type curing agents, B-882N manufactured by Mitsui Takeda Chemical Co., Ltd., Coronate 2513 manufactured by Nippon Polyurethane Industry Co., Ltd. (above block polyisocyanate), Cymel 303 manufactured by Mitsui Cytec Co., Ltd. (methylated melamine resin) ) Etc. are known. Further, a blocked carboxylic acid such as the following B-1 that protects a polycarboxylic acid that can be used as a curing agent for an epoxy resin is also known.

Radiation curable resins are roughly classified into radical curable resins and cationic curable resins. As the curable component of the radical curable resin, a compound having a plurality of radical polymerizable groups in the molecule is used. As a typical example, a polyfunctional acrylate monomer having 2 to 6 acrylate groups in the molecule And a compound having a plurality of acrylate groups in the molecule called urethane acrylate, polyester arylate, and epoxy acrylate.
As a typical curing method of the radical curable resin, there are a method of irradiating an electron beam and a method of irradiating ultraviolet rays. Usually, in the method of irradiating with ultraviolet rays, a polymerization initiator that generates radicals upon irradiation with ultraviolet rays is added. In addition, if the polymerization initiator which generate | occur | produces a radical by heating is added, it can also be used as a thermosetting resin.

  As the curable component of the cationic curable resin, a compound having a plurality of cationic polymerizable groups in the molecule is used, and as a typical curing method, a photoacid generator that generates an acid by irradiation with ultraviolet rays is added, A method of curing by irradiating with ultraviolet rays is mentioned. Examples of the cationically polymerizable compound include a compound containing a ring-opening polymerizable group such as an epoxy group and a compound containing a vinyl ether group.

  In the base film used in the present invention, different types of resins may be selected and mixed from the above-mentioned thermosetting resins or radiation curable resins, and the thermosetting resin and the radiation curable resin may be used. May be used in combination. Moreover, you may mix and use curable resin (crosslinkable resin) and the polymer which does not have a crosslinkable group.

  In the base film used in the present invention, when the curable resin (crosslinkable resin) is mixed, the solvent resistance, heat resistance, optical characteristics, and toughness of the base are obtained, which is preferable. Moreover, it is also possible to introduce a crosslinkable group into the resin used for the base film, and it may have a crosslinkable group at any position in the polymer main chain terminal, the polymer side chain, or the polymer main chain. Good. In this case, you may produce a base material, without using said general purpose crosslinkable resin together.

  When the gas barrier laminate film of the present invention is used for a liquid crystal display application or the like, the resin used is preferably an amorphous polymer in order to achieve optical uniformity. Furthermore, for the purpose of controlling the retardation (Re) and its wavelength dispersion, it is possible to combine resins having different signs of intrinsic birefringence of the resins or to combine resins having large (or small) wavelength dispersion.

  In the present invention, for the base film, lamination of different resins can be suitably used for the purpose of controlling retardation (Re) and improving gas permeability and mechanical properties. A preferred combination of different resins is not particularly limited, and any of the above-described resins can be used in combination.

  The base film used in the present invention is a plasticizer, a dye / pigment, an antistatic agent, an ultraviolet absorber, an antioxidant, an inorganic fine particle, a peeling accelerator, a leveling agent, as long as it does not impair the effects of the present invention if necessary. Resin modifiers such as inorganic layered silicate compounds and lubricants may be added.

  The base film used in the present invention may be stretched. By stretching, mechanical strength such as folding strength is improved, and there is an advantage that handling property is improved. In particular, those having an orientation release stress in the stretching direction (ASTM D1504, hereinafter abbreviated as “ORS”) of 0.3 to 3 GPa are preferable because the mechanical strength is improved. ORS is an internal stress generated by stretching inherent in a stretched film or stretched sheet.

  As the stretching method, a known method can be used. For example, a roll uniaxial stretching method, a tenter uniaxial stretching method, a simultaneous biaxial stretching method, at a temperature between 10 ° C. and 50 ° C. higher than the Tg of the resin, The film can be stretched by a sequential biaxial stretching method or an inflation method. The draw ratio is preferably 1.1 to 3.5 times.

  Although the thickness of the base film used by this invention is not specifically limited, It is preferable that it is 30-700 micrometers, It is more preferable that it is 40-200 micrometers, It is further more preferable that it is 50-150 micrometers. The haze is preferably 3% or less, more preferably 2% or less, and further preferably 1% or less. Further, the total light transmittance is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more.

Next, a method for producing a base film in the present invention will be described.
The base film in the present invention can be produced by using several methods. Specifically, after dissolving a resin and an inorganic compound in a common solvent, a method of producing a base film by coating and drying, adding an inorganic compound in a molten state, kneading, and melting A technique for producing a base film by forming a film with an extruder, a technique for producing a base film by reacting a precursor of an inorganic compound in a resin solution, and then applying and drying the resin. For example, the precursor is made into a uniform solution, then coated and dried to form a film, and an inorganic compound is generated by a reaction in the film to produce a base film.

  Among them, the base film in the present invention is preferably prepared by obtaining a metal oxide by a hydrolysis and polycondensation reaction by a sol-gel method in a resin solution, and applying and drying a solution containing the metal oxide. . Hereinafter, a method for producing a base film by a sol-gel method will be described.

  Hydrolysis and polycondensation based on the sol-gel method is a method in which a metal alkoxide compound is reacted with water to convert an alkoxy group into a hydroxyl group, and then the hydroxyl group is simultaneously polycondensed to form a hydroxy metal group. This is a reaction in which a polymer having a dehydration reaction or a dealcoholization reaction is three-dimensionally cross-linked through a covalent bond. As a starting material for the sol-gel reaction, a metal complex compound can be used instead of a metal alkoxide compound.

  As the metal alkoxide compound, when only an alkoxy group is bonded to all metal atoms, that is, not only methoxide, ethoxide, isopropoxide, etc., but also a part of which is substituted with a methyl group, an ethyl group, etc., for example, monomethyl alkoxide , Monoethyl alkoxide and the like are also included. Furthermore, the metal complex compound includes not only a case where only an acetylacetone group is bonded to all metal atoms, but also a compound in which a part thereof is substituted with a methylalkoxy group, an ethylalkoxy group or the like.

As the metal, a metal selected from the group consisting of Si, Ti, Al and Zr is preferably used. Tetramethoxysilane [Si (OCH ₃ ) ₄ ], tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ] , Methyltriethoxysilane [(CH ₃ ) Si (OC ₂ H ₅ ) ₃ ], methyltrimethoxysilane [(CH ₃ ) Si (OCH ₃ ) ₃ ], titanium tetraisopropoxide [Ti (O-iso-C ₃ H _{7) 4],} titanium acetylacetonate [Ti (CH ₃ COCHCOCH _{3) 4],} aluminum tri secondary butoxide _{[Al (O-sec-C 4} H 9) 4 ], zirconium n-butoxide [Zr (O-n -C ₄ H _{9) 4],} zirconium acetylacetonate [Zr (CH ₃ COCHCOCH _{3) 4]} and the like are preferable. From the viewpoint of reaction rate and price, alkoxysilanes are preferred, and tetraethoxysilane is particularly preferred.

Next, a specific method for obtaining silicon oxide from alkoxysilane will be described.
(A) Organosilane Organosilane represents a silane compound having a functional group capable of giving silanol by hydrolysis in the molecule. In the above metal oxide, hydrolysis obtained by hydrolysis and condensation. And / or a partial condensate, and serves as a binder in the metal oxide.
In general, a compound represented by the formula (R) ₄ Si is preferably used. In the formula, R represents a hydrocarbon group (for example, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and these groups may have a substituent), an alkoxyl group, an oxyacyl group or a halogen atom. Four Rs in one molecule may be the same as or different from each other within the scope of this definition, and can be freely selected and combined, but four do not become a hydrocarbon group at the same time. Preferably, no more than two hydrocarbon groups are simultaneously present in one molecule.

Of these organosilanes, alkoxysilanes are particularly preferably used. An example is an alkoxysilane represented by the general formula Si (OR ¹ ) _x (R ² ) _4-x . R ¹ in the alkoxysilane is preferably an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, or an n-butyl group. , Sec-butyl group, tert-butyl group, acetyl group and the like. R ² is preferably an organic group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, tert-butyl group, n-hexyl group, cyclohexyl. Group, n-octyl group, tert-octyl group, n-decyl group, unsubstituted hydrocarbon group such as phenyl, vinyl group, allyl group, etc., γ-chloropropyl group, CF ₃ CH ₂ —, CF ₃ CH _{2 CH 2 -, C 3 F 7} CH 2 CH 2 CH 2 -, H (CF 2) 4 CH 2 OCH 2 CH 2 CH 2 -, γ- glycidoxypropyl group, .gamma.-mercaptopropyl group, 3,4 Examples thereof include substituted hydrocarbon groups such as an epoxycyclohexylethyl group and a γ-methacryloyloxypropyl group. x is preferably an integer of 2 to 4.

Specific examples of these alkoxysilanes are shown below.
Examples of x = 4 (hereinafter referred to as tetrafunctional organosilane) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetraacetoxysilane, and the like. Can be mentioned.

As x = 3 (hereinafter referred to as trifunctional organosilane), methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane , Iso-propyltrimethoxysilane, iso-propyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane , Γ-methacryloyloxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, vinyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxy Cyclohexylethyl _{triethoxysilane, CF 3 CH 2 CH 2 Si} (OCH 3) 3, C 2 F 5 CH 2 CH 2 Si (OCH 3) 3, C 2 F 5 OCH 2 CH 2 CH 2 Si (OCH 3) 3 _{, C 3 F 7 OCH 2 CH} 2 CH 2 Si (OC 2 H 5) 3, (CF 3) 2 CHOCH 2 CH 2 CH 2 Si (OCH 3) 3, C 4 F 9 CH 2 OCH 2 CH 2 CH 2 Si (OCH ₃ ) ₃ , H (CF ₂ ) ₄ CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , 3- (perfluorocyclohexyloxy) propyltrimethoxysilane and the like can be mentioned.

Examples of x = 2 (hereinafter referred to as bifunctional organosilane) include dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di- n- propyl diethoxy silane, di -iso- propyl dimethoxysilane, di -iso- propyl diethoxy silane, diphenyl dimethoxy silane, divinyl diethoxy _{silane, (CF 3 CH 2 CH 2} ) 2 Si (OCH 3) 2, ( C ₃ F ₇ OCH ₂ CH ₂ CH ₂ ) ₂ Si (OCH ₃ ) ₂ , [H (CF ₂ ) ₆ CH ₂ OCH ₂ CH ₂ CH ₂ ] ₂ Si (OCH ₃ ) ₂ , (C ₂ F ₅ CH ₂ CH ₂ ) ₂ Si (OCH ₃ ) _{2 and the} like.

  Said organosilane may be used individually by 1 type, and can also use 2 or more types together.

  In the present invention, the base film can also be formed by applying and curing a solution containing organosilane prepared by the above-described method as one constituent component. In addition to these organosilanes, the following various compounds can be added to the solution as necessary.

(B) Hydrolysis / condensation catalyst (sol-gel catalyst)
(C) Solvent (d) Chelate ligand compound (e) Water (f) Other additives

  Hereinafter, various additives that can be used in combination will be described in detail.

(B) Sol-gel catalyst In the sol liquid that can be used in combination, various catalyst compounds can be used for the purpose of promoting hydrolysis / partial condensation reaction of organosilanes. The catalyst used is not particularly limited, and an appropriate amount may be used according to the constituent components of the used sol solution.
In general, the following compounds (b1) to (b5) are effective, and a preferable amount of these compounds can be added from these compounds. Further, two or more of these groups can be appropriately selected and used in combination as long as the mutual promoting effects are not inhibited.

(B1) Organic or inorganic acids Examples of inorganic acids include hydrochloric acid, hydrogen bromide, hydrogen iodide, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid, and phosphorous acid. Organic acid compounds include carboxylic acids (formic acid, acetic acid, Propionic acid, butyric acid, succinic acid, cyclohexanecarboxylic acid, octanoic acid, maleic acid, 2-chloropropionic acid, cyanoacetic acid, trifluoroacetic acid, perfluorooctanoic acid, benzoic acid, pentafluorobenzoic acid, phthalic acid, etc.), sulfone Acids (methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid), p-toluenesulfonic acid, pentafluorobenzenesulfonic acid, etc.), phosphoric acid / phosphonic acids (phosphoric acid dimethyl ester, phenylphosphonic acid, etc.), Lewis acids (three fluorocarbons) Boron bromide etherate, scandium triflate, alkyl titanic acid , Aluminate, etc.) and heteropolyacids (phosphomolybdic acid, phosphotungstic acid, etc.).

(B2) Organic or inorganic base Examples of the inorganic base include sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and ammonia. Examples of the organic base compound include amines (ethylenediamine, diethylenetriamine, triethylenetetramine). , Tetraethylenepentamine, triethylamine, dibutylamine, tetramethylethylenediamine, piperidine, piperazine, morpholine, ethanolamine, diazabicycloundecene, quinuclidine, aniline, pyridine, etc.), phosphines (triphenylphosphine, trimethylphosphine, etc.), Metal alkoxides (sodium methylate, potassium ethylate, etc.) can be mentioned.

(B3) Metal chelate compound An alcohol represented by the general formula R ¹⁰ OH (wherein R ¹⁰ represents an alkyl group having 1 to 6 carbon atoms) and R ¹¹ COCH ₂ COR ¹² (wherein R ¹¹ is carbon number 1-6 alkyl group, R ¹² is preferably not particularly limited as long as it is a metal that diketones as a ligand represented by an alkyl group or an alkoxy group having 1 to 16 carbon atoms having 1 to 5 carbon atoms) Can be used. Within this category, two or more metal chelate compounds may be used in combination.
Particularly preferred as the metal chelate compound of the present invention is one having Al, Ti, Zr as the central metal, and has the general formula Zr (OR ¹⁰ ) _p1 (R ¹¹ COCHCOR ¹² ) _p2 , Ti (OR ¹⁰ ) _q1 (R Those selected from the group of compounds represented by ¹¹ COCHCOR ¹² ) _q2 and Al (OR ¹⁰ ) _r1 (R ¹¹ COCHCOR ¹² ) _r2 are preferred and serve to promote the condensation reaction of the component (a).

R ¹⁰ and R ¹¹ in the metal chelate compound may be the same or different and each is an alkyl group having 1 to 6 carbon atoms, specifically, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, sec -Butyl group, tert-butyl group, n-pentyl group, phenyl group and the like. R ¹² represents an alkyl group having 1 to 6 carbon atoms as described above, or an alkoxy group having 1 to 16 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and n-butoxy. Group, sec-butoxy group, tert-butoxy group, lauryl group, stearyl group and the like. Moreover, p1-r2 in a metal chelate compound represents the integer determined so that it may become a 4 or 6-dentate coordination.

  Specific examples of these metal chelate compounds include tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetate). Zirconium chelate compounds such as acetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium, diiso Titanium chelate compounds such as propoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum, diisopropyl Poxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonate bis (ethyl) An aluminum chelate compound such as acetoacetate) aluminum. Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonate) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are preferable. These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, the partial hydrolyzate of these metal chelate compounds can also be used.

(B4) Organometallic compound Although there is no restriction | limiting in particular as a preferable organometallic compound, Since an organic transition metal has high activity, it is preferable. Of these, tin compounds are particularly preferred because of their good stability and activity. Specific examples of these compounds include (C ₄ H ₉ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ , (C ₄ H ₉ ) ₂ Sn (OCOCH═CHCOOC ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Carboxylic acid type organotin compounds such as Sn (OCOC ₁₁ H ₂₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH═CHCOOC ₄ H ₉ ) ₂ , Sn (OCOCC ₈ H ₁₇ ) ₂ ; (C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ CH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₁₂ H ₂₅ ) ₂ , etc., mercaptide type and sulfide type organotin compounds, (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO, or ( _{C 4 H 9) 2 SnO,} (C 8 H 17) organotin oxide and ethyl silicate dimethyl maleate, such as ₂ SnO, diethyl maleate, phthalic Organic tin compounds such as the reaction product of an ester compound such as dioctyl the like.

(B5) Metal salts As the metal salts, alkali metal salts of organic acids (for example, sodium naphthenate, potassium naphthenate, sodium octanoate, sodium 2-ethylhexanoate, potassium laurate, etc.) are preferably used. The content of the metal salt in the solution of the sol-gel catalyst compound is 0.01 to 50% by mass, preferably 0.1 to 50% by mass, more preferably 0. 0% by mass with respect to the mass of the organosilane that is the raw material of the sol solution. 5 to 10% by mass.

(C) Solvent The solvent uniformly mixes each component in the sol solution, and adjusts the solid content of the solution in the sol-gel solution, and at the same time, can be applied to various coating methods, and the dispersion stability and storage of the solution. It improves stability. These solvents are not particularly limited as long as they can fulfill the above purpose.
Preferable examples of these solvents include water, alcohols, aromatic hydrocarbons, ethers, ketones, esters, and mixed solvents thereof.

Among these, examples of the alcohols include monohydric alcohols and dihydric alcohols. Among these, monohydric alcohols are preferably saturated aliphatic alcohols having 1 to 8 carbon atoms. Specific examples of these alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol. Examples thereof include monobutyl ether and ethylene glycol monoethyl ether acetate.

  Specific examples of aromatic hydrocarbons include benzene, toluene, xylene and the like. Specific examples of ethers include tetrahydrofuran and dioxane. Specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, Specific examples of esters such as diisobutyl ketone include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate. These organic solvents can be used alone or in combination of two or more. The ratio of the organic solvent in the solution is not particularly limited, and an amount for adjusting the total solid content concentration according to the purpose of use is used.

(D) Chelate ligand compound When a metal complex compound is used in the sol solution, it is also preferable to use a compound having a chelate coordination ability from the viewpoint of adjusting the curing reaction rate and improving the liquid stability. Preferably used are β-diketones and / or β-ketoesters represented by the general formula R ¹⁰ COCH ₂ COR ^11, which act as a stability improver for the solution. That is, by coordinating with a metal atom in a metal chelate compound (preferably zirconium, titanium and / or aluminum compound) present in the accelerating liquid, the condensation reaction of component (a) by these metal chelate compounds is promoted. This is considered to suppress the action of controlling the rate of curing of the resulting film. R ¹⁰ and R ¹¹ are synonymous with R ¹⁰ and R ¹¹ constituting the metal chelate compound, but need not have the same structure when used.

  Specific examples of the β-diketones and / or β-ketoesters include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate. Acetic acid-sec-butyl, acetoacetic acid-tert-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane -Dione, 5-methyl-hexane-dione and the like can be mentioned. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketones and / or β-ketoesters may be used alone or in combination of two or more. Such β-diketones and / or β-ketoesters are used in an amount of 2 moles or more, preferably 3 to 20 moles per mole of the metal chelate compound, and if less than 2 moles, the resulting composition has poor storage stability. Become.

(E) Water Water is added to the preferred sol solution of the present invention for the hydrolysis / condensation reaction of the component (a). The usage-amount of water is 1.2-3.0 mol normally with respect to 1 mol of (a) organosilane components, Preferably it is about 1.3-2.0 mol. The sol liquid preferred in the present invention has a total solid content concentration of 0.1 to 50% by mass, preferably 1 to 40% by mass. When the solid component concentration exceeds 50% by mass, the storage stability of the solution is deteriorated, which is not preferable.

<Inorganic layer>
As the method for forming the inorganic layer of the present invention, any method can be used as long as it can form a target thin film, but sputtering, vacuum deposition, ion plating, plasma CVD, etc. are suitable. Films can be formed by the methods described in Japanese Patent Nos. 3400324, 2002-322561, and 2002-361774.

  The component of the inorganic layer is not particularly limited. For example, an oxide, nitride, or oxynitride containing one or more selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce, Ta, and the like is used. be able to. The thickness of the inorganic layer is not particularly limited, but if it is too thick, cracks due to bending stress may occur, and if it is too thin, the film is distributed in an island shape, so that the gas barrier property tends to deteriorate in any case. For such reasons, the thickness of each inorganic layer is preferably in the range of 5 to 1000 nm, more preferably 10 to 1000 nm, and most preferably 10 to 200 nm. In the present invention, when two or more inorganic layers are formed, each may have the same composition or a different composition.

In order to achieve both water vapor barrier properties and high transparency, it is preferable to use silicon oxide or silicon oxynitride as the inorganic layer. The silicon oxide is represented by SiO _x . For example, when SiO _x is used as the inorganic layer, 1.6 <x <1.9 in order to achieve both good water vapor barrier properties and high light transmittance. Is preferred. Silicon oxynitride is expressed as SiO _x N _y , and the ratio of x and y is an oxygen-rich film when importance is placed on improving adhesion, and 1 <x <2, 0 <y <1 In the case where improvement in water vapor barrier properties is important, it is preferable to use a nitrogen-rich film so that 0 <x <0.8 and 0.8 <y <1.3.

<Organic layer>
In the film of the present invention, the organic layer is formed by curing a radical polymerizable monomer having a vinyl group such as an acrylate group or a methacrylate group, or a cationic ring-opening polymerizable monomer having a cyclic ether group such as an epoxy group or an oxetanyl group. Is preferred. These monomers may be monofunctional or polyfunctional depending on the use, and both may be used in combination.
Moreover, in this invention, the organic layer may contain components other than an organic component, ie, an inorganic substance, an inorganic element, and a metal element.

  In the film of the present invention, the thickness of the organic layer is not particularly limited, but is preferably 10 to 5000 nm, and more preferably 10 to 2000 nm. If the thickness of the organic layer is 10 nm or more, an organic layer having a uniform thickness can be formed, structural defects of the inorganic layer can be efficiently filled with the organic layer, and gas barrier properties can be improved. If the thickness of the organic layer is 5000 nm or less, the organic layer is less likely to crack due to an external force such as bending, and good gas barrier properties can be maintained.

  In the film of the present invention, examples of the method for forming the organic layer include a coating method and a vacuum film forming method. Although there is no restriction | limiting in particular as a vacuum film-forming method, Film-forming methods, such as vapor deposition and plasma CVD, are preferable, and the resistance heating vapor deposition method which is easy to control the film-forming rate of an organic substance monomer is more preferable. There is no limitation on the method for crosslinking the organic monomer of the present invention, but crosslinking by electron beam or ultraviolet rays by irradiation with active energy rays is easy to attach in a vacuum chamber and high molecular weight by crosslinking reaction is rapid. It is preferable at this point.

  When the organic layer is formed by a coating method, various coating methods used so far, for example, roll coating, gravure coating, knife coating, dip coating, curtain flow coating, spray coating, bar coating, etc. Can be used.

  In the film of the present invention, the organic layer may be formed of an organic-inorganic hybrid material in combination with a hydrolysis and polycondensation reaction of a metal alkoxide. As the metal alkoxide, alkoxysilane and / or metal alkoxide other than alkoxysilane can be used. As the metal alkoxide other than alkoxysilane, it is preferable to use zirconium alkoxide, titanium alkoxide, aluminum alkoxide or the like. Moreover, inorganic fillers, such as well-known inorganic fine particles and layered silicate, can also be mixed with an organic layer as needed.

  In the step of forming the organic layer of the film of the present invention, the active energy ray in the method for crosslinking the organic substance monomer refers to radiation capable of propagating energy by irradiation with ultraviolet rays, X-rays, electron beams, infrared rays, microwaves, and the like. The type and energy can be arbitrarily selected according to the application.

The cationic ring-opening polymerization of the monomer during the formation of the organic layer of the present invention is performed by applying or vapor-depositing a composition containing the monomer, and then using a thermal polymerization initiator, contact heating with a heater, infrared rays, microwaves, etc. Start by radiant heating. When a photopolymerization initiator is used, it is started by irradiation with active energy rays. When irradiating with ultraviolet light, various light sources can be used, such as curing with mercury arc lamp, xenon arc lamp, fluorescent lamp, carbon arc lamp, tungsten-halogen radiation lamp and irradiation light by sunlight. . The irradiation intensity of ultraviolet rays is at least 0.01 J / cm ² . When curing is performed continuously, it is preferable to set the irradiation rate so that the composition can be cured within 1 to 20 seconds. In the case of curing with an electron beam, curing is performed with an electron beam having an energy of 300 eV or less, but it is also possible to cure instantaneously with an irradiation amount of 1 to 5 Mrad.

  In the film of the present invention, the laminate unit of at least one pair of inorganic layer and organic layer may be formed on one side or both sides of the base film. Further, one or more pairs of inorganic layers and organic layers may be repeatedly laminated adjacent to the above-mentioned lamination unit. When such a repeating unit is formed, it is preferably 5 units or less, preferably 2 units or less from the viewpoint of gas barrier properties and production efficiency. Moreover, when forming a repeating unit, each inorganic layer and each organic layer may have the same composition or different compositions.

<Functional layer>
The film of the present invention can further have the following various functional layers in addition to the inorganic layer and the organic layer.

(Transparent conductive layer)
As the transparent conductive layer that can be formed in the present invention, a known metal film or metal oxide film can be applied. Among these, a metal oxide film is preferable from the viewpoint of transparency, conductivity, and mechanical properties. For example, a metal oxide film such as indium oxide, cadmium oxide and tin oxide to which tin, tellurium, cadmium, molybdenum, tungsten, fluorine or the like is added as an impurity, and zinc oxide or titanium oxide to which aluminum is added as an impurity can be given. Among them, an indium oxide (ITO) thin film containing 2 to 15% by mass of tin oxide is excellent in terms of transparency and conductivity, and is preferably used. Examples of the method for forming the transparent conductive layer include methods such as vacuum deposition, sputtering, and ion beam sputtering.

  The film thickness of the transparent conductive layer is preferably 15 to 300 nm. If the film thickness is 15 nm or more, a continuous film is obtained, and sufficient conductivity is obtained. On the other hand, when the film thickness is 300 nm or less, good transparency can be maintained and the bending resistance is also good.

  The transparent conductive layer may be formed on either the base film side or the gas barrier coat layer (organic layer + inorganic layer) side as long as it is the outermost layer, but in the sense of preventing the entry of trace moisture contained in the base film. It is preferable to install on the gas barrier coat layer side.

(Primer layer)
The film of this invention can form a well-known primer layer or an inorganic thin film layer between a base film and a gas barrier layer. As the primer layer, for example, an acrylic resin, an epoxy resin, a urethane resin, a silicone resin, or the like can be used. In the present invention, an organic-inorganic hybrid layer is used as the primer layer, an inorganic vapor deposition layer or a sol-gel is used as the inorganic thin film layer. It is preferable to form a dense inorganic coating thin film by a method. As an inorganic vapor deposition layer, vapor deposition layers, such as a silica, a zirconia, an alumina, are preferable. The inorganic vapor deposition layer can be formed by a vacuum vapor deposition method, a sputtering method, or the like.

(Other functional layers)
Various known functional layers may be provided on the gas barrier coat layer (organic layer + inorganic layer) or on the outermost layer as necessary. Examples of such functional layers include optical functional layers such as antireflection layers, polarizing layers, color filters, ultraviolet absorbing layers, light extraction efficiency improving layers, mechanical functional layers such as hard coat layers and stress relaxation layers, and antistatic Examples thereof include an electrical functional layer such as a layer / conductive layer, an antifogging layer, an antifouling layer, and a printing layer.

The film of the present invention suitably has an oxygen transmission rate of 0 to 0.1 ml / m ² · day · atm at 38 ° C., 0% relative humidity and / or 90%, and 0 to 0.05 ml / m. ² · day · atm is preferable, and 0 to 0.005 ml / m ² · day · atm is more preferable. In particular, when the oxygen permeability at 38 ° C. and relative humidity of 0% and / or 90% is 0.05 ml / m ² · day · atm or less, device deterioration due to oxygen is substantially eliminated when used in an LCD. This is preferable. Further, when the oxygen permeability at 38 ° C. and relative humidity 0% and / or 90% is 0.005 ml / m ² · day · atm or less, the device is substantially deteriorated by oxygen when used in organic EL. This is preferable because it can be eliminated.

The film of the present invention suitably has a water vapor transmission rate of 0 to 0.1 g / m ² · day at 38 ° C. and a relative humidity of 90%, and 0 to 0.05 g / m ² · day. It is preferably 0 to 0.005 g / m ² · day. In particular, when the water vapor transmission rate at 38 ° C. and relative humidity of 90% is 0.05 g / m ² · day or less, it is preferable to use it for an LCD because deterioration of the element due to water can be substantially eliminated. Further, when the water vapor transmission rate at 38 ° C. and 90% relative humidity is 0.005 g / m ² · day or less, it is preferable to use it for organic EL because the deterioration of the element due to water can be substantially eliminated.

It is preferable that the film of the present invention can maintain the oxygen transmission rate and the water vapor transmission rate even after the bending treatment or the heat treatment.
The oxygen permeability after the bending test is suitably 0 to 0.1 ml / m ² · day · atm at 38 ° C. and 0% relative humidity and / or 90%. it is preferably ^{05ml / m 2 · day · atm} , even more preferably ^{0~0.005ml / m 2 · day · atm} . Further, the water vapor transmission rate after the bending test is suitably 0 to 0.1 g / m ² · day at 38 ° C. and 90% relative humidity, and 0 to 0.05 g / m ^2. · It is preferably day, and more preferably 0 to 0.005 g / m ² · day.

The oxygen permeability after the heat treatment is, for example, 0 to 0.1 ml / m ² · day · atm at 38 ° C. and 0% relative humidity and / or 90% after heat treatment at 250 ° C. it is suitable, preferably a ^{0~0.05ml / m 2 · day · atm} , even more preferably ^{0~0.005ml / m 2 · day · atm} . Further possible water vapor permeability after the bending test, 38 ° C., it is appropriate at a relative humidity of 90% which is 0~0.1g / m ² · day, a 0~0.05g / m ² · day Is preferable, and more preferably 0 to 0.005 g / m ² · day.
Similarly, after treatment at 300 ° C., the oxygen transmission rate is suitably 0 to 0.1 ml / m ² · day · atm at 38 ° C. and 0% relative humidity and / or 90%. it is preferably ^{0.05ml / m 2 · day · atm} , even more preferably ^{0~0.005ml / m 2 · day · atm} . Further possible water vapor permeability after the bending test, 38 ° C., it is appropriate at a relative humidity of 90% which is 0~0.1g / m ² · day, a 0~0.05g / m ² · day Is preferable, and more preferably 0 to 0.005 g / m ² · day.

[Organic / inorganic composite composition]
The organic / inorganic composite composition of the present invention comprises an inorganic compound and a resin having a glass transition temperature of 250 ° C. or higher. About the inorganic compound contained in the organic / inorganic composite composition of the present invention and the resin having a glass transition temperature of 250 ° C. or higher, those described in the description of the above-mentioned gas barrier laminate film can be used. The same is true for. The organic / inorganic composite composition of the present invention is a metal oxide and a polymer having a spiro structure represented by the general formula (I) or a polymer having a cardo structure represented by the general formula (II). It is preferable to contain.

The metal oxide used in the organic / inorganic composite composition of the present invention is not particularly limited as long as it is a metal oxide derived from a metal capable of forming an oxide. As described in the column, it is preferable to use a metal oxide obtained by hydrolysis and polycondensation reaction by a sol-gel method. The metal atom constituting such a metal oxide is preferably a metal atom selected from the group consisting of silicon, zirconium, aluminum, titanium, and germanium. Further, the metal oxide contained in the organic / inorganic composite composition of the present invention may be a composite oxide derived from a plurality of metal atoms.
Preferred metal oxides contained in the organic / inorganic composite composition of the present invention are silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, and germanium oxide, and more preferred are silicon oxide, aluminum oxide, and oxide. Zirconium.

  Definitions and preferred compounds of a polymer having a spiro structure represented by the general formula (I) and a polymer having a cardo structure represented by the general formula (II) that can be used in the organic / inorganic composite composition of the present invention For examples, reference can be made to the description in the description of the gas barrier laminate film.

  In the organic / inorganic composite composition of the present invention, the content mass of the metal oxide and the polymer having the spiro structure represented by the general formula (I) or the polymer having the cardo structure represented by the general formula (II) The ratio is preferably 5:95 to 70:30, more preferably 5:95 to 50:50, and even more preferably 5:95 to 30:70.

  In addition to inorganic compounds such as metal oxides and resins having a glass transition temperature of 250 ° C. or higher, a third component may be added to the organic / inorganic composite composition of the present invention depending on the solvent and purpose. Specifically, resin modifiers such as plasticizers, dyes and pigments, antistatic agents, ultraviolet absorbers, antioxidants, inorganic fine particles, peeling accelerators, leveling agents, inorganic layered silicate compounds and lubricants are added. May be. The content of the third component is preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, and 5% by mass or less. Is even more preferred.

[Plastic substrate]
The plastic substrate of the present invention is produced using the above organic / inorganic composite composition. At this time, the method similar to the manufacturing method of the base film in the column of description of said gas-barrier laminated | multilayer film can be employ | adopted, and the same structure can be employ | adopted.

  In the plastic substrate of the present invention, the metal oxide content is preferably 5% by mass to 70% by mass, more preferably 5% by mass to 50% by mass, and 5% by mass to 30% by mass. More preferably. Moreover, it is preferable that thickness is 40 micrometers-200 micrometers, it is more preferable that it is 50-150, and it is further more preferable that it is 60-120.

  The plastic substrate of the present invention preferably contains a metal oxide, so that the heat distortion temperature is preferably increased by 2 ° C or higher, more preferably increased by 5 ° C or higher, more preferably increased by 10 ° C or higher. Is more preferable. The heat distortion temperature here is measured by the method described in Examples described later. By measuring the thermal deformation temperature of the plastic substrate of the present invention containing a metal oxide and a plastic substrate having the same composition except that it does not contain any metal oxide, the difference is calculated. An increase in deformation temperature can be obtained.

  In addition, the plastic substrate of the present invention preferably has a coefficient of thermal expansion reduced by 20 ppm / ° C. or more by containing a metal oxide, more preferably by 30 ppm / ° C. or more, more preferably 40 ppm / ° C. or more. More preferably, it is lowered. A thermal expansion coefficient here is measured by the method described in the Example mentioned later. By measuring the coefficient of thermal expansion between the plastic substrate of the present invention containing a metal oxide and a plastic substrate having the same composition except that it does not contain any metal oxide, the difference is calculated. A reduction range of the expansion coefficient can be obtained.

  The plastic substrate of the present invention is excellent in optical properties and mechanical properties. Specifically, according to the present invention, a plastic substrate having a small retardation and suitable for an image forming element is provided. In addition, since the plastic substrate of the present invention is not easily deformed by heat and has excellent durability, the plastic substrate is deformed or electrically conductive by heat treatment performed after forming the transparent conductive film, or by forming an alignment film, a gas barrier film, or the like. There is no decline in sex. For this reason, the plastic substrate of this invention is preferably used for the liquid crystal display device, organic EL element, TFT array, etc. which are described below.

[Image display element]
Although the use of the film and plastic substrate of the present invention is not particularly limited, it can be suitably used as a transparent electrode substrate of an image display element because of excellent optical characteristics and mechanical characteristics. The term “image display element” as used herein means a circularly polarizing plate / liquid crystal display element, a touch panel, an organic EL element, or the like. In addition, although the following description is performed about the case where the film of this invention is applied for convenience, it is applicable similarly to the plastic substrate of this invention.

<Circularly polarizing plate>
A circularly polarizing plate can be produced by laminating a λ / 4 plate and a polarizing plate on a film of the present invention in which a transparent conductive layer is formed as a functional layer (hereinafter referred to as “film substrate”). In this case, the lamination is performed so that the slow axis of λ / 4 and the absorption axis of the polarizing plate are 45 °. As such a polarizing plate, it is preferable to use what is extended | stretched in the 45 degree direction with respect to the longitudinal direction (MD), For example, what is described in Unexamined-Japanese-Patent No. 2002-865554 can be used suitably.

<Liquid crystal display element>
The reflective liquid crystal display device has a configuration including a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film in order from the bottom. The film substrate of the present invention can be used as the transparent electrode and the upper substrate. In the case of color display, it is preferable to further provide a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.
The transmissive liquid crystal display device includes, in order from the bottom, a backlight, a polarizing plate, a λ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, a λ / 4 plate, and a polarization It has a structure consisting of a film. Among these, the film substrate of the present invention can be used as the upper transparent electrode and the upper substrate. In the case of color display, it is preferable to further provide a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.
The liquid crystal cell is not particularly limited, but more preferably TN (Twisted Nematic) type, STN (Supper Twisted Nematic) type or HAN (Hybrid Aligned Nematic) type, VA (Vertically Alignment) type, ECB type (Electrically Controlled Birefringence), OCB A type (Optically Compensatory Bend) and a CPA type (Continuous Pinwheel Alignment) are preferable.

<Touch panel>
The touch panel can be applied to those described in JP-A-5-127822, JP-A-2002-48913, and the like.

<Organic EL device>
The film of the present invention can be used for organic EL display applications as a substrate with a transparent electrode by providing TFTs as necessary. The specific layer structure of the organic EL display element is as follows: anode / light emitting layer / transparent cathode; anode / light emitting layer / electron transport layer / transparent cathode; anode / hole transport layer / light emitting layer / electron transport layer / transparent cathode Anode / hole transport layer / light emitting layer / transparent cathode; anode / light emitting layer / electron transport layer / electron injection layer / transparent cathode; anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron Examples include injection layer / transparent cathode.
When the film of the present invention is used for an organic EL device or the like, JP-A Nos. 11-335661, 11-335368, JP-A Nos. 2001-192651, 192652, No. 192653, No. 335776, No. 247859. 181616, 181617, JP-A-2002-181816, 181617, JP-A-2002-056776, and JP-A-2001-148291, 221916, 231443. It is preferable to use together with each publication of No ..
That is, the film of the present invention can be used as a base film and / or a protective film when forming an organic EL element.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

Example 1 Production and Evaluation of Gas Barrier Laminate Film Examination was performed using PES (Tg = 220 ° C.), C-3 (Tg = 270 ° C.), and FL-7 (Tg = 360 ° C.) as the resin for forming the base film .

<Film 1A: PES alone>
A PES pellet was dissolved in an N-methylpyrrolidone / dichloromethane mixed solvent (mass ratio 1/1), and a 15% solution was applied and dried to obtain a film 1A having a thickness of 100 μm.

<Film 1B: PES / Colloidal Silica = 92/8>
Snow Tech MEK-ST (manufactured by Nissan Chemical Industries, Ltd., MEK dispersion of hydrophobic colloidal silica having a diameter of about 10 nm) is added to the solution of film 1A to form a uniform solution, which is then applied and dried to give a film having a thickness of 100 μm 1B was obtained. Snow Tech MEK-ST was added so that the mass ratio of the resin / inorganic component was 92/8 after drying.

<Film 1C: PES / Colloidal Silica = 84/16>
A film 1C having a thickness of 100 μm was obtained in the same manner as the film 1B except that the resin / inorganic component mass ratio after drying was 84/16.

<Film 1D: PES / Colloidal Silica = 76/24>
A film 1D having a thickness of 100 μm was obtained by the same operation as the film 1B except that the resin / inorganic component mass ratio became 76/24 after drying.

<Film 1E: PES / Niobium pentoxide = 92/8>
Niobium (V) ethoxide and water were reacted in 2-methoxyethanol to prepare a niobium pentoxide (Nb ₂ O ₅ ) dispersion having a negative thermal expansion coefficient and a diameter of about 20 nm. The dispersion and the solution of the film 1A were mixed to obtain a uniform solution, which was then applied and dried to obtain a film 1E having a thickness of 100 μm. Niobium pentoxide was added so that the resin / inorganic component mass ratio was 92/8 after drying.

<Film 1F: PES / Niobium pentoxide = 84/16>
A film 1F having a thickness of 100 μm was obtained in the same manner as the film 1E except that the resin / inorganic component mass ratio after drying was 84/16.

<Film 1G: PES / Niobium pentoxide = 76/24>
A film 1G having a thickness of 100 μm was obtained in the same manner as the film 1E except that the resin / inorganic component mass ratio after drying was 76/24.

<Film 1H: C-3 alone>
A C-1 powder was dissolved in dichloromethane, and a 15% solution was applied and dried to obtain a film 1H having a thickness of 100 μm.

<1I: C-3 / Colloidal silica = 92/8>
Except that the PES of the film 1B was changed to the resin C-3, the same operation was performed to obtain a film 1I having a thickness of 100 μm.

<1J: C-3 / Colloidal silica = 84/16>
Except that the PES of the film 1C was changed to the resin C-3, the same operation was performed to obtain a film 1J having a thickness of 100 μm.

<Film 1K: C-3 / Colloidal Silica = 76/24>
Except having changed PES of film 1D into resin C-3, the completely same operation was performed and the film 1K with a thickness of 100 micrometers was obtained.

<Film 1L: C-3 / Niobium pentoxide = 92/8>
Except that the PES of the film 1E was changed to the resin C-3, the same operation was performed to obtain a film 1L having a thickness of 100 μm.

<Film 1M: C-3 / Niobium pentoxide = 84/16>
Except having changed PES of the film 1F into resin C-3, the completely same operation was performed and the film 1M with a thickness of 100 micrometers was obtained.

<Film 1N: C-3 / Niobium pentoxide = 76/24>
Except that the PES of the film 1G was changed to the resin C-3, the same operation was performed to obtain a film 1N having a thickness of 100 μm.

<Film 10: FL-7 alone>
The FL-10 powder was dissolved in a dichloromethane / anisole mixed solvent (mass ratio 9/1), and a 15% solution was applied and dried to obtain a film 100 having a thickness of 100 μm.

<Film 1P: FL-7 / Colloidal silica = 92/8>
Except that 1B PES was changed to Resin FL-7, the same operation was performed to obtain a film 1P having a thickness of 100 μm.

<Film 1Q: FL-7 / Colloidal silica = 84/16>
Except that the PES of the film 1C was changed to the resin FL-7, the same operation was performed to obtain a film 1Q having a thickness of 100 μm.

<Film 1R: FL-7 / Colloidal Silica = 76/24>
Except that the PES of the film 1D was changed to the resin FL-7, the same operation was performed to obtain a film 1R having a thickness of 100 μm.

<Film 1S: FL-7 / Niobium pentoxide = 92/8>
Except that the PES of the film 1E was changed to the resin FL-7, the same operation was performed to obtain a film 1S having a thickness of 100 μm.

<Film 1T: FL-7 / Niobium pentoxide = 84/16>
Except that the PES of the film 1F was changed to the resin FL-7, the same operation was performed to obtain a film 1T having a thickness of 100 μm.

<Film 1U: FL-7 / Niobium pentoxide = 76/24>
Except that the PES of the film 1G was changed to the resin FL-7, the same operation was performed to obtain a film 1U having a thickness of 100 μm.

2. Production of Samples 2A to 2U (1) Film Formation of Inorganic Layer A commercially available roll-to-roll type sputtering apparatus was used. This apparatus has a vacuum chamber, and a drum for heating or cooling the substrate film in contact with the surface is disposed at the center thereof. Moreover, the winding tank for winding a base film is arrange | positioned at the said vacuum chamber. The base film wound on the roll is wound on a drum via a guide, and further wound on a take-up roll via another guide. As a vacuum exhaust system, the vacuum chamber is always exhausted from the exhaust port by a vacuum pump. As a film forming system, a target is mounted on a cathode connected to a DC discharge power source to which pulse power can be applied. This discharge power source is connected to a controller, and this controller is further connected to a piezoelectric element valve unit that supplies the vacuum chamber while adjusting the amount of reaction gas introduced through a pipe. The vacuum chamber is configured to be supplied with a constant flow rate of discharge gas. The amount of reaction gas introduced is set so that the desired film quality can be obtained, and the discharge is sustained in the transition region. If the voltage value at this time is set as the set voltage value and the voltage value is larger than the set value, the controller sends a command to the piezoelectric element valve unit to reduce the reaction gas flow rate. If the voltage value is smaller than the set value, the controller sends a command to the piezoelectric element valve unit to increase the reaction gas flow rate. In this way, the flow rate of the reaction gas supplied to the vacuum chamber is controlled to an appropriate amount. Specific conditions are shown below.

1A-1U was used as a base film. Si was set as a target, and a pulse application type DC power source was prepared as a discharge power source. The vacuum pump was started and the inside of the vacuum chamber was evacuated to the 10 ⁻⁴ Pa level, and argon was introduced as a discharge gas and oxygen was introduced as a reaction gas. When the atmospheric pressure was stabilized, the discharge power supply was turned on, plasma was generated on the Si target with a discharge power of 5 kW, and the film formation pressure was reduced to 0.030 Pa, and then the sputtering process was started. The voltage value at this time was 610V. Using this voltage value as a set value, the controller increases the oxygen flow rate when the discharge voltage is smaller than the set value in the transition region, and decreases the oxygen flow rate when the discharge voltage is larger than the set value in the transition region. The discharge voltage was controlled to be constant by giving a command to the piezoelectric element valve unit. In this way, a 50 nm thick SiO _x layer was formed. This was designated as base film samples 2A to 2U.

(2) Formation of organic layer 12.37 g of 3-ethyl-3- [3- (triethoxysilyl) propyloxymethyl] oxetane synthesized by the method described in JP-A-2000-264969, tetramethylammonium hydroxide A 10% aqueous solution of 1.05 g, 1.14 g of water, and 300 ml of 1,4-dioxane were charged and heated to reflux for 16 hours with stirring. Next, 200 ml of the solvent was distilled off under reduced pressure to concentrate the reaction system, and the reaction was continued for 6 hours. Thereafter, the solvent and the like were distilled off under reduced pressure, and the solvent was replaced with 200 ml of toluene, followed by washing with water and dehydration to obtain the desired product. It was confirmed by GPC and NMR that an oxetanyl group-containing silsesquioxane compound having an average molecular weight (Mn) of about 2000 was obtained. 100 parts by weight of this compound (parts by mass, the same applies hereinafter) and a coating composition prepared by adding 2 parts of diphenyl-4-thiophenoxysulfonium hexafluoroantimonate as a polymerization initiator were mixed on the base film (2A to 2U). The substrate coated with a bar coating so as to have a thickness of about 4 μm was irradiated with ultraviolet rays at an irradiation intensity of 70 mJ / cm ² in the atmosphere using an ultraviolet irradiation device using a 395 W high-pressure mercury lamp [Toscure 401 manufactured by Harrison Toshiba Lighting Co., Ltd.]. Samples (3A to 3U) that were cured by irradiation with ultraviolet rays at a dose (2000 mJ / cm ² , confirmed by FT-IR) with which the composition reacted sufficiently were prepared.

(3) Deposition of second inorganic layer Samples (4A to 4U) in which an inorganic layer was installed in exactly the same manner as (1) except that a sample in which 3A to 3U was attached to a guide base as a base film were used. Produced.

(4) Production of transparent conductive layer Samples in which base films 4A to 4U were introduced into a vacuum chamber and a transparent electrode made of an IXO thin film having a thickness of 0.2 μm was formed by DC magnetron sputtering using an IXO target ( 5A-5U).

3. Bending resistance test substrate films 5A to 5U are cut into 20 cm × 30 cm, both ends are bonded to form a cylindrical shape with the barrier coat layer on the outside, and two 12 mmφ conveying rollers are applied with a tension of about 1 N between the two rollers. Then, the film was rotated and conveyed five times at 30 cm / min, taking care that the film and the roller part were completely in contact and the film did not slip. The sample was conditioned for 8 hours in an environment of 25 ° C. and a relative humidity of 60%, and the test was performed in a laboratory under the same conditions.

4). 250 ° C. Heat Test A sample was prepared by irradiating the surface of the gas barrier layer of the base film 5A to 5U with a commercially available infrared heater until the surface temperature rose to 250 ° C., and then allowing to cool to 25 ° C. The surface temperature was monitored with a commercially available radiation thermometer.

5). 300 ° C. heating test The surface of the gas barrier layer of the substrate films 5A to 5I was irradiated with a commercially available infrared heater, heated until the surface temperature rose to 300 ° C., and then allowed to cool to 25 ° C. to prepare a sample. The surface temperature was monitored with a commercially available radiation thermometer.

6). For the gas permeability samples 5A to 5U, the untreated sample, the sample after the flexibility test, the sample after the 250 ° C. heat test, the sample after the 300 ° C. heat test, 38 ° C., the oxygen permeability at 0% relative humidity, 38 ° C., Water vapor permeability at 90% relative humidity was measured by the MOCON method. The results are shown in Table 1.

It can be seen that when the sample used in this example was untreated, all of the oxygen permeability and water vapor permeability exhibited excellent gas barrier properties below the detection limit.
From the results of the bendability test, it is desirable for the content of the inorganic substance in the base film to be less than 20% by mass in order to maintain the gas barrier property even after the bendability test, and a sample having an inorganic content of 20% by mass or more ( In 5D, 5G, 5K, 5N, 5R, 5U), the gas barrier properties are lowered. This indicates that it is important to add a small amount of inorganic substance in order to give the substrate flexibility.

  In addition, from the results of the 250 ° C. heat test, the sample using PES having Tg of 220 ° C. is a gas barrier property after the 250 ° C. heat test for both the resin alone (5A) and the case of containing an inorganic compound (5B-5G). Is greatly reduced. When C-3 having a Tg of 270 ° C. and FL-7 having a Tg of 360 ° C. are used, the resin alone (5H, 5O) shows a decrease in gas barrier properties after a 250 ° C. heating test, whereas the inorganic compound is 10% by mass. In the samples (5J, 5K, 5M, 5N, 5Q, 5R, 5T, 5U) including the above, no gas barrier property deterioration after the 250 ° C. heating test is observed. In the case of a sample containing an inorganic compound having a positive coefficient of linear thermal expansion, a decrease in gas barrier properties is observed after the 250 ° C. heating test at an addition amount (5I, 5P) of less than 10% by mass, whereas negative linear heat In the case of a sample containing an inorganic compound having an expansion coefficient, a decrease in gas barrier properties is not observed even after a 250 ° C. heating test at an addition amount (5 L, 5 S) of less than 10% by mass. This indicates that in a sample containing an inorganic compound having a negative linear thermal expansion coefficient, it is possible to suppress a decrease in gas barrier properties due to heating with the addition of a small amount of the inorganic compound.

  Moreover, from the result of a 300 degreeC heating test, in the case of the sample (5A-5G) using PES which is Tg = 220 degreeC, and the sample (5H-5N) using C-3 which is Tg = 270 degreeC, either Even after the 300 ° C. heating test, the gas barrier properties are greatly reduced. On the other hand, when FL-7 with Tg = 360 ° C. is used, the resin alone (5O) shows a decrease in gas barrier properties after a 300 ° C. heating test, whereas it contains 10% by mass or more of an inorganic compound (5G ) Is not observed to decrease the gas barrier property after the 300 ° C. heating test. In the case of a sample containing an inorganic compound having a positive linear thermal expansion coefficient, a decrease in gas barrier properties is observed after the 300 ° C. heating test at an addition amount (5P) of less than 10% by mass. On the other hand, in the case of a sample containing an inorganic compound having a negative linear thermal expansion coefficient, no decrease in gas barrier properties is observed even after the 300 ° C. heating test at an addition amount (5S) of less than 10% by mass. This indicates that in a sample containing an inorganic compound having a negative linear thermal expansion coefficient, it is possible to suppress a decrease in gas barrier properties due to heating with the addition of a small amount of the inorganic compound.

  These results show that it is effective to add a small amount of inorganic material to give the substrate flexibility, and it is effective to add a large amount of inorganic material to maintain gas barrier properties after heat treatment. Is shown. Compared with an inorganic compound having a positive linear thermal expansion coefficient, an inorganic compound having a negative linear thermal expansion coefficient can maintain a gas barrier property after heat treatment with a small amount of addition. It is preferable from the viewpoint of compatibility. In order to maintain the gas barrier property after the heat treatment, it is effective to use a resin having a Tg equal to or higher than the heating temperature.

(Example 2) Production and evaluation of organic EL device using gas barrier laminate film Preparation of Organic EL Element Aluminum lead wires were connected from the transparent electrodes (IXO) of the base films 5P to 5U to form a laminated structure. The surface of the transparent electrode was spin-coated with an aqueous dispersion of polyethylene dioxythiophene / polystyrene sulfonic acid (BAYER, Baytron P: solid content 1.3 mass%), and then vacuum-dried at 150 ° C. for 2 hours to a thickness of 100 nm. The hole transportable organic thin film layer was formed. This was made into the board | substrates 6P-6U.
On the other hand, a coating solution for a light-emitting organic thin film layer having the following composition was formed on one surface of a temporary support made of 188 μm thick polyethersulfone (Sumilite FS-1300 manufactured by Sumitomo Bakelite Co., Ltd.) using a spin coater. The luminescent organic thin film layer having a thickness of 13 nm was formed on the temporary support by applying and drying at room temperature. This was designated as transfer material Y.

Polyvinylcarbazole (Mw = 63000, manufactured by Aldrich): 40 parts by mass Tris (2-phenylpyridine) iridium complex (orthometalated complex): 1 part by mass Dichloroethane: 3200 parts by mass

The light-emitting organic thin film layer side of the transfer material Y is placed on the upper surface of the organic thin film layers of the substrates 7P to 7U, and heated and pressurized at 160 ° C., 0.3 MPa, 0.05 m / min using a pair of heat rollers, and temporarily supported. By peeling off the body, a light-emitting organic thin film layer was formed on the upper surface of the substrate X. This was designated as substrates 8P to 8U.
Further, a patterned evaporation mask (a mask with a light emitting area of 5 mm × 5 mm) is placed on one side of a polyimide film (UPILEX-50S, manufactured by Ube Industries) having a thickness of 50 μm cut into 25 mm square, and about 0. Al was evaporated in a reduced pressure atmosphere of 1 mPa to form an electrode having a film thickness of 0.3 μm. LiF was deposited in the same pattern as the Al layer by DC magnetron sputtering using a LiF target to a film thickness of 3 nm. Aluminum lead wires were connected from the Al electrode to form a laminated structure. A coating solution for an electron transporting organic thin film layer having the following composition is coated on the obtained laminated structure with a spin coater coating machine, and vacuum dried at 80 ° C. for 2 hours, whereby an electron transporting organic film having a thickness of 15 nm is obtained. A thin film layer was formed on LiF. This was designated as substrate Z.

１−ブタノール： ３５００質量部 Polyvinyl butyral 2000L (Mw = 2000, manufactured by Denki Kagaku Kogyo): 10 parts by mass Electron transporting compound having the following structure: 20 parts by mass

1-butanol: 3500 parts by mass

  Using the substrates XY and Z, the electrodes are stacked so that the electrodes face each other with the light-emitting organic thin film layer interposed therebetween, and heated and pressurized at 160 ° C., 0.3 MPa, 0.05 m / min using a pair of heat rollers, The organic EL elements 9P to 9U were obtained by bonding.

2. Evaluation of organic EL element Next, the obtained organic EL elements 9P to 9U were made to emit light by applying a DC voltage to the organic EL element using a source measure unit 2400 type (manufactured by Toyo Technica Co., Ltd.). Both organic EL elements emitted light well. When the device was allowed to stand for 1 month at 25 ° C. and 75% relative humidity after the device was fabricated and light was emitted in the same manner, all emitted good light.
Furthermore, after repeating the operation of winding the light emitting surface of a separately prepared organic EL element using a 12 mmφ roller and extending it to a flat surface 5 times, after leaving it to stand at 40 ° C. and 90% relative humidity for 10 days, light is emitted in the same manner. As a result, the organic EL elements 9P, 9Q, 9S, and 9T similarly showed good light emission. On the other hand, the organic EL elements 9R and 9U were obviously deteriorated because the area of the non-light emitting portion exceeded 80%. The difference due to the base film is presumed to be because the base film having excellent flexibility contributes to preventing slight deterioration of the laminated barrier layer.

Example 3 Production and Evaluation of Plastic Substrate Production of Resin (I-7) Polyester resin (I-7) was obtained by the following method.

To a solution in which 6.16 g of M-101 is suspended in 40 ml of methylene chloride, 75 ml of water in which 0.06 g of sodium hydrosulfite and 0.56 g of tetrabutylammonium bromide are dissolved is added and stirred vigorously. did. Thereto, 21 ml of a 2 mol / liter NaOH aqueous solution and a 20 ml methylene chloride solution of 4.18 g of 1,4-cyclohexane dichloride were simultaneously added at room temperature over 1 hour. After the addition, the reaction was further performed for 6 hours, and then the organic layer was separated by a liquid separation operation. Further, it was washed twice with 300 ml of diluted hydrochloric acid, and methylene chloride was distilled off under reduced pressure. To the residue, methylene chloride was added and dissolved, and after removing dust and filtering, it was slowly put into 200 ml of methanol. The precipitated resin was collected by filtration, washed with methanol, and dried to obtain 7.42 g of Resin (I-7) as a white solid. The number average molecular weight of the obtained resin was 42000, and Tg was 221 ° C.
Here, the monomer (M-101) having a spirobiindane skeleton can be produced by a known method. That is, it can be produced by the method described in, for example, US Pat. No. 3,544,638 and JP-A-62-10030.

2. Production of Resin (C-1) Polycarbonate resin (C-1) was obtained by the following method.

200 ml of 0.28 g of M-103, 52.7 mg of tert-butylphenol dissolved in 225 ml of methylene chloride in which 0.2 g of hydrosulfite sodium and 17.8 g of sodium hydroxide were dissolved Of water was added and stirred vigorously. Thereto was added a solution of 6.92 g of triphosgene in 25 ml of methylene chloride over 30 minutes. After the addition, the reaction was further continued for 1 hour, and then 0.2 ml of triethylamine was added. After further 4 hours of reaction, the organic layer was separated by a liquid separation operation. Further, it was washed twice with 300 ml of diluted hydrochloric acid, and methylene chloride was distilled off under reduced pressure. 80 ml of methylene chloride was added to the residue and dissolved, and after removing dust and filtering, it was slowly put into 400 ml of methanol. The precipitated resin was collected by filtration, washed with methanol, and dried to obtain 15.7 g of resin (C-1) as a white solid. The number average molecular weight of the obtained resin was 86000, and Tg was 214 ° C.
Here, the monomer (M-103) having a spirobichroman skeleton can be produced by a known method. That is, it can be produced by the method described in, for example, Journal of Chemical Society, Vol. 111, page 4953 (1989), JP-A-62-130735.

3. Tetrahydrofuran was added to 4.0 g of the resin (I-7) produced in the production of the plastic substrate to prepare a solution having a concentration of 10% by mass. After filtering this solution through a 5 μm filter, 1.0 g of phenyltrimethoxysilane and 0.1 g of 0.1 mol / liter hydrochloric acid were added, and the mixture was stirred at 25 ° C. for 2 hours. Subsequently, the obtained solution was cast on a glass substrate using a doctor blade. After casting, the film was dried by heating at 80 ° C. for 2 hours and 120 ° C. for 8 hours, and then the film was peeled from the glass substrate to produce a plastic substrate F-101. Also, plastic substrates F-102 to F-104 were produced in the same manner except that the resin and metal oxide precursor were changed to the ratios shown in Table 2 below. Table 2 also shows the plastic substrate F-101.
Similarly, resin (C-1), resin (C-2), resin (I-14), and commercially available polycarbonate (manufactured by Teijin Chemicals, Panlite L1225Z) were used in the same manner except that they were changed to the amounts shown in Table 2 below. Thus, plastic substrates F-105 to F-110 were produced. However, when panlite was used, it was prepared using a solvent in which tetrahydrofuran and N, N-dimethylformamide were mixed at a volume ratio of 1/4 instead of tetrahydrofuran.

4). Physical properties of the plastic substrate ratings plastic substrate F-101~F-110 thickness, appearance, and the in-plane direction retardation values are shown in Table 3. Moreover, TMA measurement and tensilon measurement of the obtained film were performed by the following method. Here, as a comparison, plastic substrates F-1111 to F-113 in which no metal oxide is added to Resin (I-7), Resin (C-1), and Resin (I-14) are prepared, and the results are also described. did.
<Mechanical properties of film>
A film sample (1.0 cm × 5.0 cm piece) was prepared and measured with Tensilon (manufactured by Toyo Baldwin Co., Ltd., Tensilon RTM-25) under the condition of a tensile speed of 3 mm / min. Three samples were measured, and the average value was obtained (the sample was used after standing overnight at 25 ° C. and 60% RH. The distance between chucks was 3 cm).
<Linear thermal expansion coefficient (CTE) of film>
A film sample (0.5 cm × 2.0 cm piece) was prepared and measured by a tensile load method of TMA (manufactured by Rigaku Corporation, TMA8310) under a tensile load of 100 mN.
<Retardation>
The retardation value at a film in-plane direction and a wavelength of 632.8 nm was measured with an automatic birefringence meter (manufactured by Oji Scientific Instruments, KOBRA-21ADH) and calculated according to the following formula.
Formula: Retardation = | nMD-nTD | × d
[NMD: refractive index in the film width direction, nTD: refractive index in the film longitudinal direction, d: thickness]

  From the results shown in Table 3, it can be seen that the plastic substrate produced from the resin of the present invention has a small retardation value and excellent optical characteristics. Furthermore, it can be seen that the plastic substrate obtained from the organic / inorganic composite composition of the present invention has an improved thermal deformation temperature and a low thermal expansion. Further, all of the plastic substrates of the present invention had good transparency with a haze of 1% or less and a total light transmittance of 88% or more.

Example 4 Production and Evaluation of Image Display Element Production of display element substrate <gas barrier layer>
On both surfaces of the plastic substrate shown in Table 3, the DC magnetron sputtering method, under a vacuum of target the Si0 ₂ 500 Pa, an Ar atmosphere, and sputtering at an output 5 kW. The film thickness of the obtained gas barrier layer was 60 nm.

<Transparent conductive layer>
While heating the substrate thus obtained to 100 ° C., ITO (95% by mass of In ₂ O ₃ and 5% by mass of SnO ₂ ) was used as a target by DC magnetron sputtering under an Ar atmosphere under a vacuum of 0.665 Pa. Below, sputtering was performed at an output of 5 kW, and a transparent conductive layer made of an ITO film having a thickness of 140 nm was provided on one side.

<Protective layer>
On the barrier layer, a coating solution having the following formulation is stirred and dissolved at room temperature, and then coated with a bar coater to a thickness of 3 μm (after drying), heated at 80 ° C. for 10 minutes, and then irradiated with ultraviolet light. Was irradiated.
Acrylic resin (glass transition point 105 ° C., molecular weight 67000, acid value 2 acrylic (Mitsubishi Rayon LR-1065)); 100 parts by mass Silane coupling agent (Shin-Etsu Chemical KBM-573; N- Phenyl-γ-aminopropyltrimethoxysilane); 1 part by mass / butyl acetate; 400 parts by mass

2. Evaluation of Image Display Element Substrate The surface resistance of the thus prepared image display element substrate (plastic substrate with a transparent conductive layer) was measured by the method of JIS-C-2141. Further, the surface resistance after the heat treatment at 250 ° C. was also measured, and the appearance after the heat treatment was also observed.

  It can be seen from Table 4 that the image display device substrate of the present invention is not easily changed by heat and has excellent durability.

Moreover, the following is understood from the results of Tables 3 and 4.
The plastic substrate obtained from the organic / inorganic composite composition of the present invention is excellent in optical properties and has a small thermal expansion coefficient. In addition, the decrease in mechanical strength due to the organic / inorganic composite is small and superior to conventional resins. Furthermore, the image display element substrate obtained from the plastic substrate of the present invention is not easily deformed by heat, and has durability that cannot be achieved by an organic / inorganic composite composition obtained from a conventional resin.

3. Fabrication of image display device <Circular fabrication of circularly polarizing film>
On the opposite side of the transparent conductive layers of the image display device substrates F-101, F-103, F-105, F-107 and Comparative Examples F-111, F-112, F-113 of the present invention, A λ / 4 plate described in JP-A-826705 and JP-A-2002-131549 was laminated, and a polarizing plate described in JP-A-2002-865554 was further laminated thereon to produce a circularly polarizing plate. The angle between the transmission axis of the polarizing film and the slow axis of the λ / 4 plate was set to 45 °.

<Production of TN liquid crystal display device>
Image display element substrates F-101, F-103, F-105, and F-107 of the present invention, and comparative examples F-111, F-112, and F-113 and an aluminum reflective electrode on which fine irregularities are formed A polyimide alignment film (SE-7992, manufactured by Nissan Chemical Industries, Ltd.) was formed on the transparent conductive (ITO) layer and the electrode side of the provided glass substrate, respectively. Although heat treatment was carried out at 200 ° C. for 30 minutes, no increase in resistance value or gas permeability was observed in the present invention. On the other hand, all the comparative examples increased more than twice.
This was rubbed, and two substrates (a glass substrate and a plastic substrate) were stacked with a 1.7 μm spacer so that the alignment films face each other. The orientation of the substrate was adjusted so that the rubbing directions of the two alignment films intersected at an angle of 110 °. Liquid crystal (MLC-6252, manufactured by Merck) was injected into the gap between the substrates to form a liquid crystal layer. In this way, a TN liquid crystal cell having a twist angle of 70 ° and a Δnd value of 269 nm was produced.
A reflection type liquid crystal display device was prepared by laminating the λ / 4 plate and the polarizing plate on the surface opposite to the ITO of the image display element substrate. Good images were obtained using the image display device substrate of the present invention. On the other hand, in the case of using the comparative example, a black spot failure due to a decrease in gas barrier properties (a fine black spot is not displayed on the image layer portion and an image is not displayed) and a color shift due to a crack in the conductive layer occurred.

<Production of STN type liquid crystal display device>
Transparent conductivity of a glass substrate in which the substrate for image display element F-101, F-103, F-105, F-107 of the present invention and Comparative Examples F-111, F-112, F-113 and an ITO layer are laminated ( A polyimide alignment film (SE-7992, manufactured by Nissan Chemical Industries, Ltd.) was formed on the ITO layer side. Although heat treatment was performed at 200 ° C. for 30 minutes, no increase in resistance value or increase in gas permeability was observed in the present invention. On the other hand, all the comparative examples increased more than twice. The two substrates were stacked with a 6.0 μm spacer so that the alignment films face each other. The orientation of the substrate was adjusted so that the rubbing directions of the two alignment films intersected at an angle of 60 °. Liquid crystal (ZLI-2777, manufactured by Merck & Co., Inc.) was injected into the gap between the substrates to form a liquid crystal layer. Thus, an STN type liquid crystal cell having a twist angle of 240 ° and a Δnd value of 791 nm was produced.
The λ / 4 plate and the polarizing plate were laminated on the glass substrate side of the liquid crystal cell, and a light guide plate and a light source were placed thereunder. The λ / 4 plate and the polarizing plate were laminated on the plastic substrate side to obtain a transmissive liquid crystal display device. Good images were obtained using the plastic substrate of the present invention. On the other hand, in the case of using the comparative example, a black spot failure (a fine black dot is not displayed on the image layer portion and an image is not displayed) due to a decrease in gas barrier property, or a color shift due to a crack in the conductive layer occurred. In addition, these generation rates are the ratios of the generation regions when they are assembled on the liquid crystal display substrate to display the entire surface in white and visually shown as a ratio to the total display area.

<Production of organic EL element>
The plastic substrates F-101, F-103, F-105, and F-107 of the present invention are sequentially protected from the observer side according to Japanese Patent Laid-Open No. 2000-267097 (with an antireflection functional layer on the outermost surface) / the above circle The polarizing plate (the ITO layer of the plastic substrate of the present invention is on the organic EL side) / organic EL element / reflecting electrode. The thing of this invention showed the favorable performance.

<Production of TFT array>
A TFT array was fabricated from the plastic substrates F-101, F-103, F-105, and F-107 of the present invention according to the method described in JP-T-10-512104. Even when exposed to dimethyl sulfoxide as a resist removal solvent and a photolithography developer during the production process, no change such as fogging was observed.

  The film of the present invention has excellent durability, heat resistance and gas barrier performance, and can maintain excellent gas barrier performance even if it is flexible, so that it can be suitably used for various image display elements, particularly organic EL. it can.

Claims (16)

  An organic / inorganic composite composition comprising an inorganic compound and a resin having a glass transition temperature of 250 ° C. or higher. The organic resin according to claim 1, wherein the resin is a polymer having a spiro structure represented by the following general formula (I) or a polymer having a cardo structure represented by the following general formula (II). Inorganic composite composition.

[In general formula (I), ring α represents a monocyclic or polycyclic ring, and the two rings are connected by a spiro bond. ]

[In general formula (II), ring β and ring γ represent a monocyclic or polycyclic ring, and two rings γ may be the same or different from each other. Linked to quaternary carbon. ]   The organic / inorganic composite composition according to claim 1, wherein the inorganic compound is a metal oxide obtained by hydrolysis and polycondensation reaction by a sol-gel method.   The organic / inorganic composite composition according to claim 1, wherein the inorganic compound has a negative linear expansion coefficient.   The organic atom according to any one of claims 1 to 4, wherein the metal atom constituting the metal oxide is a metal atom selected from the group consisting of silicon, zirconium, aluminum, titanium, and germanium. Inorganic composite composition.   The plastic substrate which consists of an organic-inorganic composite composition as described in any one of Claims 1-5.   7. The plastic substrate according to claim 6, wherein the metal oxide content is 5 mass% to 70 mass% and the thickness is 40 μm to 200 μm.   8. The plastic substrate according to claim 6, wherein the thermal deformation temperature is increased by 2 ° C. or more by containing a metal oxide. 9.   The plastic substrate according to any one of claims 6 to 8, wherein a thermal expansion coefficient is reduced by 20 ppm / ° C or more by containing a metal oxide.   A plastic substrate with a transparent conductive layer, comprising a transparent conductive layer on the plastic substrate according to claim 6.   A gas barrier laminate film in which at least one set of inorganic layer and organic layer is formed on a base film containing an inorganic compound, wherein the base film is a film made of a resin having a glass transition temperature of 250 ° C. or higher. A gas barrier laminate film characterized by that.   The gas barrier laminate film according to claim 11, wherein the inorganic compound is a metal oxide obtained by hydrolysis and polycondensation reaction by a sol-gel method.   The gas barrier laminate film according to claim 11 or 12, wherein the inorganic compound has a negative linear expansion coefficient. The base film is a film made of a polymer having a spiro structure represented by the following general formula (I) or a polymer having a cardo structure represented by the following general formula (II). The gas barrier laminate film according to one item.

[In general formula (I), ring α represents a monocyclic or polycyclic ring, and the two rings are connected by a spiro bond. ]

[In general formula (II), ring β and ring γ represent a monocyclic or polycyclic ring, and two rings γ may be the same or different from each other. Linked to quaternary carbon. ]   The gas barrier laminate film according to any one of claims 11 to 14, wherein the base film is the plastic substrate according to any one of claims 6 to 10.   The image display element using the plastic substrate as described in any one of Claims 6-10, or the gas-barrier laminated film as described in any one of Claims 11-15 as a board | substrate.