JP2013004377A - Organic thin film, gas barrier film, adhesive film, display device, and film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic thin film having a high gas barrier capability, a gas barrier film and an adhesive film comprising the organic thin film, a display device using the organic thin film, a film having the organic thin film, and a display device having the film.SOLUTION: An organic thin film at least has: a first organic molecular skeleton layer 2; a network layer 3 laminated on the first organic molecular skeleton layer 2; and a second organic molecular skeleton layer 4 laminated on the network layer 3. An organic molecular skeleton configuring the network layer 3 is coupled in an in-plane direction, or alternatively, a long axis of the organic molecular skeleton configuring the network layer is oriented in the in-plane direction, and an interval in the in-plane direction, of the organic molecular skeleton configuring the network layer, is smaller than intervals in the in-plane direction, of the first and second organic molecular skeletons.

Description

  The present invention relates to an organic thin film comprising a plurality of molecular skeletons, a gas barrier film and an adhesive film comprising the organic thin film, a display device using the organic thin film, a film comprising the organic thin film, and a display device comprising the film.

In recent years, an organic semiconductor device using an organic material as a main component has been attracting attention because it can be made flexible, lighter, and lower in cost than a conventional inorganic semiconductor device. The organic material can be dissolved in a solvent, and a thin film can be formed using a solution process such as an inkjet method, a spin coating method, or a casting method. Therefore, it is possible to fabricate elements on a large area substrate and to increase the area of a display, and it does not damage a plastic substrate with low heat resistance. Therefore, a flexible device has been difficult with conventional inorganic semiconductor materials. Expectation is expected to be realized.
Recently, practical use of organic semiconductor devices has begun to appear, such as the production of organic EL displays. However, there is a problem in stably driving the device for a long time. The cause of the deterioration of organic devices is that water molecules and oxygen molecules penetrate into the organic semiconductor thin film and chemically react with charged organic semiconductor molecules (radical ions) when the device is driven, losing its original characteristics. Can be mentioned. In order to prevent the intrusion of water molecules and oxygen molecules, a method for covering the surface of the substrate on which the organic device is formed with a gas barrier film is being developed.
In order to achieve high gas barrier properties, it is difficult to use a film made of only a single material, and a gas barrier film formed by laminating a plurality of materials having different functions has been considered. However, when dissimilar materials are laminated, the thermal expansion coefficient differs between the materials, so that there is a problem of peeling between layers due to heating during the process, and the elastic coefficient and mechanical strength between the materials differ, so that the organic device itself is flexible. There was a problem of becoming a barrier to the transformation.
In recent years, as a technique for improving adhesiveness, a gas barrier film in which an adhesive layer in which layers are connected by a chemical bond is inserted has been proposed (for example, Patent Document 1).

Moreover, not only a gas barrier film but a molecular adhesive is known as a material for directly connecting different kinds of materials by chemical bonds (Patent Document 2). A molecular adhesive as described in Patent Document 2 generally has a functional group that binds to each substrate at both ends of the molecule, and steadily connects the upper layer and the lower layer with a monomolecular film via the molecule. Therefore, it has a feature of excellent adhesiveness.

JP 2008-143098 A JP 2008-50541 A

  However, in the adhesive layer provided between the upper layer and the lower layer, as described in Patent Document 1, a molecule (a silane coupling agent in Patent Document 1) that chemically connects the upper layer and the lower layer. In the case where the silane coupling agent is dispersed, all the reactive groups of the silane coupling agent are not exhibited on the surface layer of the adhesive layer, so that the bonding points between the silane coupling agent and the upper layer or the lower layer are reduced. Moreover, in patent document 1, an upper layer and a lower layer will couple | bond indirectly through the high molecular compound formed by a silane coupling agent condensing. In addition, since the molecular arrangement and bonding state are not strictly controlled when the adhesive layer is formed, phase separation or the like may occur, and there may be a region with a dense molecular density in the film. The region where the molecular density is sparse may be a pinhole that allows gas to pass between the upper layer and the lower layer. In addition, even when many organic molecules are mixed to increase the number of bonding points, there is a possibility that unevenness or density in the adhesive layer may occur due to aggregation of the organic molecules. As a result, there was still room for improvement in the adhesion and gas barrier properties of the gas barrier film described in Patent Document 1.

  Further, when a molecular adhesive as described in Patent Document 2 is used for bonding a plurality of different materials, an improvement in adhesion is recognized, but the gas barrier capability of the adhesive layer itself is low. In general, when a monomolecular film such as a molecular adhesive is formed by chemical bonding, the molecular density in the monomolecular film is determined by the position and interval of the bonding point of the lower layer to which the molecule is bonded, and the size and shape of the molecule. . In other words, it is difficult to arrange molecules at high density unless an appropriate combination of attachment points and molecule sizes is selected. For this reason, when a normal molecular adhesive is used, there is a space between the molecules that is large enough to allow oxygen and water to permeate between the upper and lower layers. Since oxygen and water permeate between the upper layer and the lower layer through the gap, it is difficult to use the molecular adhesive itself of Patent Document 2 as a gas barrier film. Even if molecular adhesives can be arranged at a high density, the molecules interact with each other with a weak force called van der Waals force, and a similar void is generated between the molecules due to thermal motion. Use on membranes was difficult.

  The present invention has been made in view of the above circumstances, and comprises an organic thin film comprising a plurality of molecular skeletons and having a high gas barrier ability, an adhesive film comprising the organic thin film, a gas barrier film comprising the organic thin film, and the organic thin film It aims at providing the display apparatus using this, the film provided with this organic thin film, and the display apparatus provided with this film.

As a result of diligent research to solve the above problems, the present inventors have made use of the intermolecular skeleton bond and the bulky molecular skeleton orientation to provide a gap between the molecular skeletons constituting the film, that is, in-plane. It was found that an organic thin film having a high gas barrier capability can be obtained by providing a layer having a narrow gap between molecules in the direction, and this layer becomes a bottleneck for gas permeation, thereby completing the present invention.
That is, the present invention provides an organic thin film having the following characteristics, a gas barrier film and an adhesive film made of the organic thin film, a display device using the organic thin film, a film including the organic thin film, and a display device including the film. Is.

(1) Organic having at least a first organic molecular skeleton layer, a network layer laminated on the first organic molecular skeleton layer, and a second organic molecular skeleton layer laminated on the network layer The thin film is formed by bonding a plurality of organic molecular skeletons constituting the network layer in the in-plane direction, or the long axis of the organic molecular skeleton constituting the network layer is oriented in the in-plane direction. And the spacing in the in-plane direction of the organic molecular skeleton constituting the network layer in the in-plane direction is larger than the spacing in the in-plane direction of the first organic molecular skeleton and the second organic molecular skeleton. An organic thin film characterized by being small.
(2) The organic thin film according to (1), wherein the first organic molecular skeleton and the second organic molecular skeleton are bonded to the organic molecular skeleton constituting the network layer by a chemical bond.
(3) Furthermore, it has a second network layer laminated on the second organic molecular skeleton layer, and a third organic molecular skeleton layer laminated on the second network layer, The organic molecular skeleton constituting the second network layer is bonded in the in-plane direction, or the long axis of the organic molecular skeleton constituting the second network layer is oriented in the in-plane direction, and The distance in the in-plane direction of the organic molecular skeleton constituting the second network layer in the in-plane direction is larger than the distance in the in-plane direction of the second organic molecular skeleton and the third organic molecular skeleton. The organic thin film according to (1) or (2), wherein the organic thin film is small.
(4) At least one of the first organic molecular skeleton layer and the second organic molecular skeleton layer is a monomolecular layer in which single organic molecules are formed side by side (1) to (3) Any organic thin film.
(5) The organic thin film according to any one of (1) to (4), wherein the first organic molecular skeleton and the second organic molecular skeleton include a linear alkane skeleton.
(6) The organic thin film according to (5), wherein the first organic molecular skeleton and the second organic molecular skeleton are linear alkane skeletons, and the organic molecular skeleton constituting the network layer is a naphthalene skeleton.
(7) The first organic molecular skeleton and the second organic molecular skeleton are linear alkane skeletons,
The organic thin film according to (5) or (6), wherein the network layer is bonded by a siloxane bond, bonded by a diacetylene group crosslinking reaction, or has a polyacrylic acid skeleton.
(8) A gas barrier film comprising at least a base material and the organic thin film of any one of (1) to (7).
(9) An adhesive film comprising the organic thin film of any one of (1) to (7) sandwiched between at least two substrates and connected to atoms on the surface of the substrate by chemical bonds.
(10) A substrate, a transistor provided on the substrate, a liquid crystal, an organic electroluminescence or electrophoretic pixel electrically connected to the transistor, and a sealing body that seals the transistor and the pixel And the display apparatus provided with the base material which coat | covers the said sealing body surface WHEREIN: The said sealing body and the said base material are pasted together through the organic thin film in any one of (1)-(7). A display device characterized by comprising:
(11) A film comprising the organic thin film according to any one of (1) to (7) and a substrate, wherein an organic molecular skeleton on the surface of the organic thin film and atoms on the surface of the substrate are bonded by chemical bonding.
(12) A substrate, a transistor provided on the substrate, a liquid crystal, an organic electroluminescent or electrophoretic pixel electrically connected to the transistor, and the substrate, the transistor, and the pixel A display device comprising a gas barrier film, wherein the gas barrier film comprises the film of (11).

The organic thin film of the present invention comprises a plurality of organic molecular skeleton layers, that is, at least two organic molecular skeleton layers, and a network layer is provided between the molecular skeleton layers. Or the orientation of the molecular skeleton constituting the network layer is the in-plane direction, and the interval between the molecular skeletons constituting the network layer is defined between the first molecular skeletons. And by making it narrower than the interval between the second molecular skeletons, the network layer can inhibit the passage of gas molecules from the vertical direction with respect to the organic thin film of the present invention, and is high. Gas barrier ability can be shown.
In addition, since the organic thin film of the present invention has a plurality of layers each made of an organic molecule, the similarity of the skeleton of the material in the organic thin film and the affinity compared to the case of only inorganic molecules or a combination of inorganic molecules and organic molecules High flexibility and flexibility, preventing delamination in the organic thin film, and making the organic thin film suitable for flexible devices.
Furthermore, since the organic thin film of the present invention is composed of an organic molecular skeleton, it can be easily bonded to other substrates by chemical bonding or the like, so that it has excellent adhesion.

It is a schematic diagram which shows an example of the organic thin film of this invention. It is a schematic diagram which shows an example of the organic thin film of this invention. It is a schematic diagram of the film of the 1st aspect of this invention. It is a schematic process drawing which shows the first half of the manufacturing method of the film of the 1st aspect of this invention. It is a schematic process drawing which shows the second half of the manufacturing method of the film of the 1st aspect of this invention. It is a schematic diagram of the film of the 2nd aspect of this invention. It is a schematic process drawing which shows the manufacturing method of the film of the 2nd aspect of this invention. It is a schematic diagram of the film of the 3rd aspect of this invention. It is a schematic process drawing which shows the manufacturing method of the film of the 3rd aspect of this invention. (A) Chemical structure, (b) Molecular model sectional view from the horizontal direction with respect to the substrate, (c) Molecular model sectional view from the direction perpendicular to the substrate of the film of the third aspect of the present invention It is. (A) chemical structure before cross-linking the network layer in the film of the third aspect of the present invention, (b) molecular model cross-sectional view from the horizontal direction with respect to the substrate, and (c) perpendicular to the substrate. It is a molecular model sectional view from a direction. It is a schematic diagram of the film of the 4th aspect of this invention. It is a schematic process drawing which shows the manufacturing method of the film of the 4th aspect of this invention. It is a schematic diagram of the film of the 5th aspect of this invention. It is a schematic process drawing which shows the manufacturing method of the film of the 5th aspect of this invention. It is a schematic diagram of the display apparatus of the 6th aspect of this invention. It is a schematic diagram which shows the manufacturing method of the display apparatus of the 6th aspect of this invention. It is a schematic diagram of the display apparatus of the 7th aspect of this invention. It is a schematic diagram which shows the manufacturing method of the display apparatus of the 7th aspect of this invention.

<Organic thin film>
The organic thin film of the present invention includes at least a first organic molecular skeleton layer, a network layer laminated on the first organic molecular skeleton layer, and a second organic molecular skeleton layer laminated on the network layer. And have. Hereinafter, specific examples of the organic thin film having the above configuration will be described with reference to the drawings. The organic thin film of the present invention is not limited to the following specific examples.

The organic thin film 1 according to the first embodiment shown in FIGS. 1 and 2 includes a first organic molecular skeleton layer 2, a network layer 3 laminated on the first organic molecular skeleton layer 2, and a laminated layer on the network layer 3. Second organic molecular layer 4 formed. The organic molecular skeleton constituting the network layer 3 is formed by bonding in the in-plane direction as shown in FIG. 1, or the long axis of the organic molecular skeleton constituting the network layer 3 as shown in FIG. Are aligned in the in-plane direction, and in the in-plane direction, the spacing in the in-plane direction of the organic molecular skeleton constituting the network layer 3 is in-plane with the first organic molecular skeleton and the second organic molecular skeleton. Each of the configurations will be described in detail below.

The organic molecular skeleton constituting the first organic molecular skeleton layer 2 is not particularly limited, and the first organic molecular skeleton layer is usually selected from the organic molecular skeletons used for forming a layer made of organic molecules. 2 can be selected as appropriate in consideration of the gas barrier property required for 2 and the combination with the organic molecules constituting the second organic molecular skeleton layer 4 or the network layer 3.
The organic molecular skeleton of the first organic molecular skeleton layer 2 may be aliphatic or aromatic. The first organic molecular skeleton layer 2 is preferably a monomolecular layer in which single organic molecules are formed in a single layer. Since the film thickness is uniform due to the monomolecular layer in which organic molecules are arranged in a single layer, the effect of being able to combine a plurality of organic molecular skeletons constituting the network layer with high probability in the in-plane direction, and the organic molecular skeleton This produces the effect of arranging in the in-plane direction.

Specific examples of the first organic molecular skeleton layer 2 having an aliphatic organic molecular skeleton include those containing an aliphatic hydrocarbon group as a main skeleton. In the present invention, “aliphatic” is a relative concept with respect to aromatics, and means a group or a compound having no aromaticity.
The aliphatic hydrocarbon group may be saturated or unsaturated, but is usually preferably saturated. Further, the aliphatic hydrocarbon group may be chain-like or cyclic.
The chain aliphatic saturated hydrocarbon group may be linear or branched.
Examples of the linear aliphatic saturated hydrocarbon group include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group. A linear hydrocarbon group represented by — (CH ₂ ) _p — such as a methylene group (wherein p is an integer of 1 to 20) is preferable. Among these, the linear aliphatic saturated hydrocarbon group is preferably a long-chain alkyl group having 10 to 20 carbon atoms.
As the branched aliphatic saturated hydrocarbon _{group, - [C (CH 3)} 2] q -, - [C (CH 3) (CH 2 CH 3)] q -, - [C (CH 3) ( CH ₂ CH ₂ CH ₃ )] _q -,-[C (CH ₂ CH ₃ ) ₂ ] _q- (wherein q is an integer of 1 to 20), alkylmethylene groups, alkylethylene Group, alkyltrimethylene group, alkyltetramethylene group and the like are preferable.

Examples of the cyclic aliphatic hydrocarbon group include a group obtained by removing two hydrogen atoms from a monocycloalkane such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and a polycycloalkane such as decalin, adamantane, and norbornane. Examples include groups in which two atoms have been removed.
In the aliphatic hydrocarbon group, part or all of the hydrogen atoms thereof may be substituted with a substituent. Examples of the substituent include a halogen atom such as a fluorine atom and a chlorine atom; a halogenated alkyl group in which part or all of the hydrogen atom is substituted with the halogen atom; an oxygen atom and the like. Further, when the aliphatic hydrocarbon group is cyclic, it may have a chain alkyl group as a substituent. Examples of the chain alkyl group include a methyl group, an ethyl group, a propyl group, and a t-butyl group.
In addition, in the aliphatic hydrocarbon group, a part of the carbon atoms constituting the skeleton and the ring are —O—, —C (═O) —, —C (═O) —O—, —O—C ( = O) -O-, -NH-, -C (= O) -NH-, -NH-C (= O) -O-, -NH-C (= O) -NH-, -S-,- It may be substituted with a hetero atom-containing linking group such as S—S—. Among them, it has an amide bond (—C (═O) —NH—), a urethane bond (—NH—C (═O) —O—), and a urea bond (—NH—C (═O) —NH—). And those having a sulfide bond (—S—) or a disulfide bond (—S—S—) are adjacent to each other in an in-plane organic molecular skeleton, and each has a hydrogen bond or a sulfur-sulfur bond. Therefore, the molecular density in the first organic molecular skeleton layer can be improved. As a result, the gap between molecules in the first organic molecular skeleton layer is narrowed, so that the first organic molecular skeleton layer 2 having higher gas barrier ability can be obtained.

  In particular, the first organic molecular skeleton layer 2 having an aliphatic organic molecular skeleton preferably includes a linear hydrocarbon group having 10 to 20 carbon atoms as a main skeleton. By using a linear hydrocarbon group having 10 to 20 carbon atoms, a support (a substrate on which a device to be described later is formed, an outermost surface of the device, a film substrate, etc.) between adjacent hydrocarbon groups in the layer Since the Van der Waals force in the direction parallel to the matrix on which the organic thin film is formed is improved, it is possible to form a film having a high molecular density because the molecules are likely to associate and align (for example, Porter et al., “Spontaneously organized). molecular assemblies 4. Structural characteristics of n-alkyl thiol monolayers on gold by optical lipometry, and infrared spectroscopy chemistry "Journal of American Chemical Society 1987 year, No. 109, see p.3559-68). Thereby, since the gap between molecules in the first organic molecular skeleton layer is narrowed, the first organic molecular skeleton layer 2 having higher gas barrier ability can be obtained.

As the first organic molecular skeleton layer 2 whose molecular skeleton is aromatic, one containing an aromatic hydrocarbon ring or an aromatic heterocycle (aromatic heterocycle) as a main skeleton is preferable.
Excluding two hydrogen atoms bonded to two different carbon atoms constituting benzene, toluene, xylene, mesitylene, indene, naphthalene, anthracene, phenanthrene, naphthacene, pentacene, hexacene, etc. Or a group formed by repeating these groups.
Aromatic heterocycles include, for example, furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, indole, purine, quinoline, isoquinoline, hydrogen atoms bonded to two different carbon atoms And a group formed by repeating these groups.

Among them, the first organic molecular skeleton layer 2 in the present invention preferably has an aliphatic main skeleton, more preferably a linear alkane skeleton, and a linear alkane skeleton having 10 to 20 carbon atoms. More preferably it is.
By using a linear alkane skeleton having 10 to 20 carbon atoms, not only a film having a high molecular density as described above can be formed, but also the organic molecular skeleton constituting the first organic molecular skeleton layer 2 can be formed on the support. Can be arranged in a substantially vertical direction. As a result, a reactive group can be presented at the end opposite to the support of the organic molecular skeleton, and the first organic molecular skeleton and the organic molecular skeleton constituting the network layer 3 are reliably chemically bonded. Can be formed.
In addition, by using a straight-chain alkane skeleton having 10 to 20 carbon atoms, a film with high flatness is obtained because the molecular density is high and the organic molecular skeleton is arranged in a substantially vertical direction. As a result, the orientation of the organic molecular skeleton constituting the network layer can be easily controlled, and the organic molecular skeleton can be reliably arranged in the in-plane direction. As a result, the effect of facilitating the formation of chemical bonds in the network layer and the effect of easily narrowing the interval between the organic molecular skeletons can be produced, and the gas barrier ability can be improved. Details of the method for forming the first organic molecular skeleton layer 2 will be described later.

  As described above, the organic molecular skeleton constituting the network layer 3 is formed by bonding the organic molecular skeleton constituting the network layer 3 in the in-plane direction or by aligning the organic molecular skeletons close to each other. If it becomes difficult to pass gas through the network layer 3 by forming, it will not specifically limit.

Specifically, the organic molecular skeleton constituting the network layer 3 bonded in the in-plane direction is specifically an organic molecular skeleton obtained by a chemical reaction in the in-plane direction, and a polymer main chain obtained in advance by a polymerization reaction. An organic molecular skeleton in which are arranged in the in-plane direction.
Specific examples of organic molecular skeletons obtained by chemical reaction in the in-plane direction include siloxane bonds, ethylene-acetylene bonds, ester bonds, amide bonds, urethane bonds, urea bonds, ether bonds, carbon-carbon bonds, etc. Examples include an organic molecular skeleton that forms a bond.
Examples of the organic molecular skeleton in which the polymer is arranged include a polyacrylic acid skeleton, a polymethacrylic acid skeleton, a polyethylene skeleton, a polyvinyl alcohol skeleton, a polyamine skeleton, and a polyurethane skeleton.
As shown in FIG. 1, when the network layer 3 is bonded in the in-plane direction to form a network, each organic molecular skeleton in the first organic molecular skeleton layer and the second organic molecular skeleton layer through which gas passes is formed. Since the gap is separated and becomes a barrier for the passing gas, the permeation of gas can be effectively blocked. Note that there are some gaps between the organic molecular skeletons constituting the network layer 3 bonded in the in-plane direction, and there is a possibility that gas molecules pass through the gaps. As compared with the case where no is formed, this becomes a bottleneck for gas permeation and an excellent gas barrier ability is achieved. In addition, the gap and the majority of the gaps between the first organic molecular skeletons and the gaps between the second organic molecular skeletons are not considered to be aligned in a direction perpendicular to the surface. The passage path when the molecules pass becomes long, and the gas barrier ability can be sufficiently exhibited.

Further, the organic molecular skeleton constituting the network layer 3 formed by bonding in the in-plane direction or being oriented and close to each other is not particularly limited, and the first organic molecular skeleton layer 2 and the second organic molecular skeleton layer 2 It can be determined appropriately according to the skeleton of the organic molecular skeleton layer 4. Specifically, the organic molecular skeleton capable of satisfying such requirements has a relatively rigid skeleton, and is bulky and horizontal (in-plane) compared to the organic molecular skeleton of the first organic molecular skeleton layer 2. ) Molecular skeleton arranged in the direction). Specifically, it preferably has an aromatic skeleton, and is a naphthalene skeleton substituted at least one of the 1-position, 4-position, 5-position or 8-position, for example, the 1-position of the naphthalene ring And the functional group of the first organic molecular skeleton are combined, the long axis of the naphthalene skeleton can be aligned in the horizontal direction. In addition to the naphthalene skeleton, those in which the major axes of anthracene, naphthacene, and pentacene are arranged in the horizontal direction are also preferable.
As shown in FIG. 2, the organic molecular skeleton constituting the network layer 3 is oriented in the in-plane direction, and the interval (gap) between the organic molecular skeletons constituting the network layer 3 is narrow, whereby the network layer 3 Becomes a barrier when gas molecules pass from the first organic molecular skeleton layer 2 side or the second organic molecular skeleton layer 4 side, and thus the passage of gas molecules can be suitably blocked or suppressed. Here, the diameter of each gas molecule is oxygen molecule: about 0.34 nm, water molecule: about 0.39 nm, carbon dioxide molecule: about 0.33 nm, nitrogen molecule: about 0.36 nm, methane molecule: 0.38 nm, Considering that methanol molecules are about 0.4 nm, the distance between organic molecular skeletons constituting the network layer 3 is preferably about 0.3 nm or less. In addition, it is conceivable that the permeating gas molecules exist not only as a single molecule but also as an aggregate of a plurality (2 to 4) of molecules. A great effect can be given to the suppression of permeation of light.

  The organic molecules constituting the second organic molecular skeleton layer 4 are not particularly limited, and the same organic molecular skeleton as that described for the first organic molecular skeleton 2 can be used. The first organic molecular skeleton 2 and the second organic molecular skeleton 4 may be the same or different.

  The organic thin film 1 of the present invention may have a first organic molecular skeleton layer 2, a network layer 3, a second organic molecular skeleton layer 4, and layers other than those described above. Specifically, for example, as in a second embodiment described later, a second network layer stacked on the second organic molecular skeleton layer, and a third organic layer stacked on the second network layer. It may have a molecular skeleton layer. Here, the second network layer has the same physical properties as the network layer 3, that is, is an organic molecular skeleton constituting the second network layer bonded in the in-plane direction. Or the orientation of the organic molecular skeleton constituting the second network layer is in the in-plane direction, and the interval between the organic molecular skeletons constituting the second network layer is the second organic molecular skeleton. It is preferable that the distance is smaller than the distance between the third organic molecular skeletons. The second network layer can be the same as the network layer 3, and the third organic molecular skeleton layer is the same as the first organic molecular skeleton layer 2 and the second organic molecular skeleton layer 4. Things can be used. As described above, by having a plurality of network layers in the film thickness direction, the number of layers that suppress and block gas permeation increases, so that a film with higher gas barrier ability can be obtained.

The method for producing the organic thin film 1 of the present invention is not particularly limited. Specifically, for example, an organic molecule for forming the first organic molecular skeleton layer 2 is formed on a suitable support. The first organic molecular skeleton layer 2 is laminated and formed by a known method such as a solution immersion method, a gas phase reaction method, a spin coating method, a dip coating method, or a Langmuir Blodget method, and then the network layer 3 is formed. The organic layer for forming the network layer 3 or the network layer 3 capable of forming a network is formed by the same method as described above, and the organic molecule for forming the second organic molecular skeleton layer 4 is used as described above. The organic thin film 1 shown in FIGS. 1-2 is obtained by laminating and forming the second organic molecular skeleton layer 4 by the above method.
Further, between the support and the first organic molecular skeleton layer 2, between the first organic molecular skeleton layer 2 and the network layer 3, and between the network layer 3 and the second organic molecular skeleton layer 4, It is preferable that it is couple | bonded by the chemical bond. By bonding by chemical bonding, bonding between layers becomes strong, delamination in the organic thin film can be prevented, and an organic thin film suitable for a flexible device can be obtained.

Specific examples of the support used when producing the organic thin film 1 will be described later as a film substrate.
As an organic molecule for forming the first organic molecular skeleton layer 2 used when the organic thin film 1 is produced, a functional group capable of chemically reacting with an atom on the support surface at one end of the first organic molecular skeleton. And having a functional group capable of chemically reacting with the functional group or skeleton of the network layer 3 at the other end.

As an organic molecule for forming the network layer 3 used when the organic thin film 1 is manufactured, a molecular skeleton constituting the network layer has a chemical reaction with a functional group or skeleton of the first organic molecular skeleton layer 2 at one end. And a functional group capable of chemically reacting with the functional group or skeleton of the second organic molecular skeleton layer 4 at the other end.
Further, when the organic molecular skeleton forming the network layer 3 is bonded in the in-plane direction, the organic molecules for forming the network layer 3 used in the manufacturing are those bonded in advance. You may use it, and the thing which can form a coupling | bonding in the surface simultaneously with formation of the precursor layer which can become this network layer, or after forming may be used. Specific examples of the former include those in which the network layer 3 is formed using an organic molecule (polymer) that has been polymerized in advance by a polymerization method such as radical polymerization. As a specific example of the latter, in the case where an in-plane direction bond is formed simultaneously with a precursor layer that can become the network layer 3 using an organic molecule before chemical bonding or an organic molecule before cross-linking reaction, As the organic molecule to be formed, those having many silane coupling sites such as chlorosilyl group, methoxysilyl group, ethoxysilyl group and the like are preferable, and a method of dehydrating (poly) condensing the silane coupling site can be mentioned. The reaction between the organic molecules may be a self-polymerization reaction, a self-crosslinking reaction, a reaction to which a reaction initiator is added, or a polymerization or a cross-linking reaction by application of light or heat.
In addition, when a network layer is formed by performing a reaction such as polymerization or crosslinking after forming a precursor layer that can become the network layer 3, the network layer precursor layer and another layer (for example, the second layer) The organic molecular skeleton layer 4 or the like) is subjected to a reaction such as polymerization or crosslinking. The method of applying light or heat for polymerization or crosslinking is not particularly limited, and can be performed by a conventional method according to the type of organic molecules for forming the network layer 3. For example, when a network layer 3 formed by using organic molecules having a diacetylene group as a material and bonded by a cross-linking reaction of a diacetylene group is formed, the organic molecule is dispersed in a suitable solvent and the first After coating on the organic molecular skeleton layer 2 or further forming the second organic molecular skeleton layer 4 on the network layer 3, the diacetylene site is crosslinked by irradiating a UV lamp or the like, and acetylene- An ethylene bond can be formed to form the network layer 3.

As an organic molecule for forming the second organic molecular skeleton layer 4 used when the organic thin film 1 is manufactured, the second organic molecular skeleton chemically reacts with the functional group or skeleton of the network layer 3 at one end thereof. The thing which has a functional group which can be mentioned.
The organic molecules as described above may be synthesized or commercially available.

  The organic thin film of the present invention has gas barrier ability and can be used in various applications where gas barrier properties are required. For example, the organic thin film of the present invention is produced on a device requiring gas barrier properties and used as a gas barrier film of the device; or a film generally used as a gas barrier film (for example, an aluminum oxide film, a silicon oxide film) Etc.) and an organic device can be used as an adhesive film having a gas barrier function. Moreover, the organic thin film of this invention can also be produced on a suitable base material, and can also be used as a film with a base material. Details of these will be described later.

≪Gas barrier film≫
The gas barrier film of the present invention comprises at least a base material and the above-described organic thin film of the present invention. Since the gas barrier film of the present invention covers the outermost layer surface of a substrate or a device formed on the substrate with the organic thin film of the present invention, high gas barrier performance, thin film formation and flexibility can be achieved. It is possible to improve the gas barrier ability of a gas that penetrates into a precision device, particularly an organic device that requires the above.
When the gas barrier film of the present invention is formed on an organic device or the like, the outermost layer in contact with the device or the substrate of the gas barrier film of the present invention reacts with atoms of the adherend (for example, the outermost layer of the device). It is preferable that the organic thin film and the member to be bonded are bonded by chemical bonding. By bonding by chemical bonding, the adhesion between the member to be bonded and the gas barrier film can be improved.
Here, the chemical bond is not particularly limited, but when a hydroxyl group is exposed on the surface of a member to be bonded (for example, a support, a base material, etc.), that is, a glass substrate or an ITO electrode is disposed. In the case of an adherend member such as a substrate exposed on the electrode surface or a resin member on the substrate surface, a siloxane bond, a phosphate ester bond, an ester bond, or a sulfonate ester bond is preferably used as the chemical bond. . In this case, the organic molecule for forming the organic molecular skeleton layer has a silane coupling group, a phosphonic acid group, a carboxylic acid group, or a sulfonic acid group at the terminal in contact with the bonded member. The above bond can be formed between the members. Further, when the member to be bonded is made of gold, silver, copper, platinum or the like, it is preferable to use a sulfide bond. In this case, the organic molecule for forming the organic molecular skeleton layer has a thiol group at the terminal in contact with the adherend member, so that a sulfide bond can be formed with the adherend member. In addition, when the member to be bonded is charged with a positive charge or a negative charge, it is preferable to use an ionic bond, and an organic molecule for forming the organic molecular skeleton layer is attached to the terminal contacting the member to be bonded. An ionic bond can be formed by having a charge opposite to that of the adhesive member. Further, when a functional group having hydrogen such as an amino group, a carboxyl group, a hydroxyl group, or an amide group is exposed on the surface of the adherend member, it is preferable to use a hydrogen bond, and an organic molecular skeleton layer is formed. When the organic molecule for forming has a functional group having hydrogen at the end in contact with the adherend member, a hydrogen bond can be formed.

≪Adhesive film≫
The adhesive film of the present invention comprises the above-described organic thin film of the present invention sandwiched between at least two substrates and connected to atoms on the surface of the substrate by chemical bonds. That is, the base material which consists of arbitrary combinations among members, such as a base material, the board | substrate with which the device is formed, and the outermost surface layer of this device, is adhere | attached with the organic thin film of this invention mentioned above. Since the adhesive film of the present invention can achieve high gas barrier ability, thin film thickness and flexibility by using the organic thin film of the present invention, it is suitable for precision devices, particularly organic devices, which require gas barrier properties. It can be used and the gas barrier ability of the gas which penetrates into the device can be improved.
When the organic thin film is used as an adhesive film, the outermost layer surfaces on both sides of the organic thin film have a group or structure that reacts and bonds with the atoms of the adherend member, and the organic thin film and the adherend member are bonded by chemical bonding. It is preferable that they are bonded. Examples of the chemical bond include those described above. By bonding by chemical bonding, the adhesion between the member to be bonded and the adhesive film can be improved.

≪Display device 1≫
An example of the display device of the present invention includes a substrate, a transistor provided over the substrate, a liquid crystal, an organic electroluminescence or electrophoretic pixel electrically connected to the transistor, the transistor and the pixel. In a display device including a sealing body to be sealed and a base material that covers the surface of the sealing body, the sealing body and the base material are bonded to each other via the organic thin film of the present invention described above. Display device (hereinafter referred to as “display device 1”). By using the thin film of the present invention for the display device 1, the gas barrier property of oxygen or water vapor entering the display device is enhanced, and the adhesion between the sealing body and the base material is enhanced, thereby producing a display element. Separation in the process and application to flexible devices becomes possible.
The substrate, the transistor, the pixel, and the sealing body are not particularly limited, and those usually used for display devices can be used.
As for the organic thin film of this invention used for the display apparatus 1, it is preferable that one surface is chemically bonded with the atom of the sealing body surface, and the other surface is chemically bonded with the atom of the base-material surface. Examples of the chemical bond include the same ones as described above.

≪Film≫
The film of the present invention preferably comprises the above-described organic thin film of the present invention and a substrate, and the organic molecular skeleton on the surface of the organic thin film and atoms on the surface of the substrate are preferably bonded by chemical bonding. The film of the present invention can be used as a gas barrier film, and the gas barrier ability can be imparted to the device by adhering the film to the surface of the device that requires gas barrier properties.
It does not specifically limit as a base material, The base material normally used as a base material of a film can be used. Specifically, resin materials such as polyethylene naphthalate (PEN), polyvinyl alcohol (PVA), polyethylene terephthalate (PET), and polyester (PE) can be used. In addition, when the entire film of the present invention is used as a gas barrier film, a metal material having a gas barrier ability such as gold, silver, copper, platinum, aluminum, aluminum oxide, iron or the like is also preferable as a base material.
The base material may be provided only on one side of the organic thin film, or may be provided on both sides of the organic thin film.
The chemical bond between the substrate and the organic thin film is not particularly limited, and examples thereof include the same chemical bonds as described above.

<< Display device 2 >>
Another example of the display device of the present invention includes a substrate, a transistor provided over the substrate, a liquid crystal, an organic electroluminescence or electrophoretic pixel electrically connected to the transistor, the substrate, and the transistor And the display apparatus provided with the gas barrier film provided on the said pixel is a display apparatus (henceforth "display apparatus 2") in which the said gas barrier film consists of the film of this invention mentioned above.
By using the film of the present invention for the display device 2, the gas barrier property of the display device can be easily improved by simply attaching the film, and oxygen and water vapor that cause deterioration of the device can be prevented.
The substrate, the transistor, or the electrophoretic pixel is not particularly limited, and those usually used in a display device can be used. The method of sticking the film of the present invention on these is not particularly limited, and can be performed by a conventional method.
When the film of the present invention used for the display device 2 is the outermost layer of the display device, the film of the present invention is provided with a substrate on both sides, or on the film of the present invention affixed to the display device 2 Furthermore, it is preferable to form a base material.

  Hereinafter, embodiments of the present invention will be described using specific examples, but the present invention is not limited to the following embodiments.

[First embodiment / film]
A specific example of the film of the first aspect will be described with reference to the schematic diagram of FIG.
The film 20A of the first embodiment shown in FIG. 3 is composed of a first organic molecular skeleton layer 2 composed of a linear alkane (octadecane), a network layer 3 bonded by a siloxane bond, and a linear alkane (octadecane). It is a film comprising an organic thin film 1A of the present invention comprising a second organic molecular skeleton layer 4, a substrate 11 comprising PEN, and a substrate 12 comprising aluminum oxide. One surface of the organic thin film 1A is bonded to the substrate 11 via a chemical bond 13 that is a siloxane bond, and the other surface of the organic thin film 1A is bonded to the substrate 12 via a chemical bond 14 that is a phosphonate bond. Has been.

In the first aspect, by using a siloxane bond in the network layer 3, molecules are chemically bonded to each other three-dimensionally in the in-plane direction and in the film thickness direction, and gas molecules pass through the network layer 3 and the organic thin film 1A. Can be suppressed. Further, in this embodiment, as will be described later, organic molecules having a large number of chlorosilyl groups per molecule (molecules represented by the formula (2)) are used as organic molecules forming the network layer 3 so that they are adjacent in the in-plane direction. The organic molecules to be bonded can be bonded to each other, and a network of siloxane bonds can be formed in multiple layers in the film thickness direction. Such a multilayer network is effective in blocking gas molecules.
Even if the network layer 3 has defects such as pinholes, and the gas layer permeation cannot be completely prevented only by the network layer, the portion where the gas permeates is extremely small, and the network layer 3 is a bottleneck for gas permeation. Therefore, transmission is suppressed. Further, as shown in FIG. 5, since the first organic molecular skeleton and the second organic molecular skeleton form a stone wall structure through the network layer, the passage route (pathway) for the gas molecules to pass through the organic thin film 1A. ) Is complicated and long. Therefore, it is considered that the permeation of gas molecules can be suppressed and the gas barrier ability is improved.

Furthermore, in the first aspect, since the base materials 11 and 13 and the organic thin film 1A are bonded by chemical bonding, the adhesion between the base materials 11 and 13 and the organic thin film 1A is high, and they may be peeled off. Absent.
In addition, by using a linear alkane having a relatively long carbon number as the first organic molecular skeleton layer 2 and the second organic molecular skeleton layer 4, the first organic molecular skeleton layer 2 and the second organic molecular skeleton The layer 4 can be arranged in a direction substantially perpendicular to the base materials 11 and 13, and the chemical bonds 12 and 14 can be reliably formed. Furthermore, the first organic molecular skeleton layer 2 and the second organic molecular skeleton layer 4 are arranged so that the surface of the first organic molecular skeleton layer is highly flat and the network layer 3 is well bonded in the in-plane direction. And the gas barrier property by the network layer 3 is enhanced.
The film 20A of the first aspect can be manufactured as follows, for example. Moreover, the schematic process drawing of a manufacturing method is shown to FIGS.

1. Preparation of base material After preparing the PEN film of the base material 11 and washing the surface, UV / O ₃ treatment is performed to expose hydroxyl groups on the surface.

2. Step of forming first organic molecular skeleton layer 2 The film of step 1 is immersed in a methylene chloride solution of the molecule represented by formula (1) in FIG. A chemical bond 13 composed of a siloxane bond is formed by reacting with the silane coupling site in the molecule represented by (1).
The formation of the monomolecular film composed of the molecule represented by the formula (1) can be confirmed from the increase in the peak derived from the 1s orbital of carbon by performing surface elemental analysis of XPS. Further, by using FT-IR (ATR method), it can be confirmed that an alkyl chain and an ethylene site are present on the film surface.

3. Terminal functional group modifying step The ethylene bond at the molecular end represented by the formula (1) is converted into a functional group capable of crosslinking reaction. Specifically, the ethylene site is oxidized to a hydroxyl group by immersing the membrane of Step 2 in an aqueous solution in which potassium permanganate, sodium periodate, and potassium carbonate are mixed at room temperature for 1 hour. In addition, although it is also possible to use the material which used the hydroxyl group for the terminal beforehand, the molecule | numerator which has a silane coupling part like the molecule | numerator represented by Formula (1) is a hydroxyl group and a silane coupling part. In order to cause self-polymerization, it is desirable to convert the functional group after forming a monomolecular film.
Moreover, it can confirm that the ethylene site | part was converted into the hydroxyl group from the disappearance of the peak derived from an alkyl chain and an ethylene site | part, and the appearance of the peak derived from a hydroxyl group from FT-IR (ATR method).

4). Step of forming network layer 3 A siloxane bond network is formed by reacting the chlorosilyl group of the molecule represented by formula (2) in FIGS. 4 to 5 with the hydroxyl group of the molecule adjacent in the monomolecular film in the horizontal direction. To do. Specifically, the film of step 3 is immersed in an anhydrous toluene solution of the molecule represented by formula (2) at room temperature for 1 hour. Since the molecule represented by the formula (2) has many bonding points in one molecule, a plurality of adjacent molecules of the formula (1) can be bonded by one molecule. Further, since the molecules represented by the formula (2) self-polymerize to form a siloxane bond, a plurality of networks extending in the in-plane direction are formed in the film thickness direction. By forming this network, it is possible to suppress the permeation of gas molecules, thereby improving the gas barrier ability.
Since the chlorosilyl group is easily hydrolyzed to generate a silanol group, the outermost surface of the film obtained in the above step is covered with a silanol group (SiOH).
The formation of the siloxane bond can be confirmed from an increase in the peak derived from the 2p orbital of silicon by analyzing the surface element of XPS.

5. Second organic molecular skeleton layer 4 forming step By performing the same step as the above step 2, a second monomolecular film composed of the silanol group on the surface of the network layer 3 and the molecule represented by the formula (1) is formed. To do. Furthermore, by performing the same process as the process 3, the hydroxyl group is exposed on the surface of the second layer.
At this time, the organic molecular skeletons of the first layer and the second layer are connected by a chemical bond via the surface of the network layer 3 formed in step 4. Since the silanol group of the network layer 3 is in a random position, the organic molecular skeleton in the second layer is not directly above the organic molecular skeleton in the first layer, and is likely to be bonded at a slightly shifted position. A stone wall structure can be created by the organic molecular skeleton of the second and second layers. When such a stone wall structure is formed, the gap between the organic molecular skeletons of the first and second layers is separated, so the path through which the gas passes is complicated and the distance becomes longer, so the gas barrier performance is improved. To do.

6). Substrate 12 and Bonded Functional Group Exposure Step A phosphonic acid site that forms a chemical bond 14 with the aluminum oxide thin film of the substrate 12 is exposed on the membrane surface. Specifically, the carboxylic acid active ester portion of the molecule represented by the formula (3) in FIG. 5 is reacted with the hydroxyl group on the film surface, and the film surface has three layers composed of the molecule represented by the formula (3). Lay the eyes. As the conditions for the lamination, an aqueous solution of the molecule represented by the formula (3) is prepared, and the film produced in Step 5 is immersed in the aqueous solution at room temperature for about 5 hours. The formation of a monomolecular film composed of the molecule represented by the formula (3) can be confirmed from the appearance of a peak derived from the 2s orbital of phosphorus by performing XPS surface elemental analysis. In addition, if the functional group which can form a chemical bond with the base material 12 can be exposed by the process 5, this process is unnecessary. However, when it is difficult to prepare a molecule chemically bonded to the silanol group obtained in Step 4 and having phosphonic acid, a lamination reaction is performed as in this step.

7). Formation process of base material 12 On the surface of the film obtained in process 6, aluminum oxide is formed to a thickness of 100 nm by sputtering. By performing the above steps, a chemical bond 14 composed of a phosphate ester bond is formed between the phosphonic acid site on the film surface and aluminum oxide, and a gas barrier film 20A is obtained.

The gas barrier film 20A obtained as described above has the structure shown in FIG. 5 and can exhibit a good gas barrier ability by including the network layer 3 bonded in the in-plane direction. The gas barrier ability can be measured for oxygen and moisture permeability by a known method using, for example, a known gas permeability measuring device as shown in Patent Document 1.
In addition, the gas barrier film obtained as described above has the structure shown in FIG. 5 and is bonded to the base materials 11 and 12 by chemical bonding to provide strength as a film. The thin film 1A is difficult to peel off. The adhesiveness between the base materials 11 and 12 and the organic thin film 1A can be confirmed by a peel test using a known cellophane tape.

[Second embodiment / film]
The specific example of the film of a 2nd aspect is demonstrated using the schematic diagram of FIG.
The film 20B of the second embodiment shown in FIG. 6 includes a first organic molecular skeleton layer 2 made of linear alkane (octadecane), a network layer 3 bonded by a siloxane bond, and a first layer made of linear alkane (octadecane). An organic thin film 1B of the present invention comprising a second organic molecular skeleton layer 4, a second network layer 3 ′ bonded by a siloxane bond, and a third organic molecular skeleton layer made of linear alkane (octadecane); It is a film provided with the base material 11 which consists of, and the base material 12 which consists of aluminum oxide. One surface of the organic thin film 1B is bonded to the substrate 11 via a chemical bond 13 that is a siloxane bond, and the other surface of the organic thin film 1B is bonded to the substrate 12 via a chemical bond 14 that is a phosphonate bond. Has been.

In the second aspect, in addition to the configuration and effects of the first aspect, by providing a plurality of network layers based on siloxane bonds, the permeation of gas molecules can be more effectively suppressed, and the gas barrier ability is further improved. To do.
The film 20B of the second aspect can be manufactured as follows, for example. Moreover, the schematic process drawing of a manufacturing method is shown in FIG.

1. Preparation of substrate The process up to Step 5 of the first embodiment is performed to expose hydroxyl groups on the film surface.
2. Step of forming second cross-linked layer By performing the same step as step 4 of the first embodiment, cross-linking by a siloxane bond is performed using the molecule represented by formula (2) in FIG.
3. Step of forming chemical bond with substrate 12 By performing steps 5 to 7 of the first aspect, monolayers of the third and fourth layers are formed, and further, aluminum oxide of substrate 12 and the film surface The gas barrier film 20B is manufactured by forming a phosphate ester bond with phosphonic acid.
4). Evaluation and comparison of gas barrier properties The gas permeability of the gas barrier film of the second aspect is higher than that of the gas barrier film of the first aspect having only one cross-linked layer because it has a plurality of network layers composed of siloxane bonds. Indicates. That is, the organic thin film of this embodiment has a structure in which the first organic molecular skeleton layer 2, the network layer 3, the second organic molecular skeleton layer 4, the network layer 3 ′, and the third organic molecular skeleton layer are sequentially stacked. As a result, there are a plurality of network layers that are gas permeation bottlenecks in the film thickness direction, and further, a pathway through which gas passes is more complicated, so that further improvement in gas barrier performance is realized.

[Third Aspect / Film]
A specific example of the film of the third aspect will be described with reference to the schematic view of FIG.
The film 20C of the third embodiment shown in FIG. 8 includes a first organic molecular skeleton layer 2 made of a linear alkane (decane), a network layer 3 bonded by an acetylene-ethylene bond, and a linear alkane (decane). It is a film provided with the organic thin film 1C of the present invention comprising the second organic molecular skeleton layer 4 comprising, a substrate 11 comprising PVA, and a substrate 12 comprising a gold thin film. One surface of the organic thin film 1C is bonded to the substrate 11 via a chemical bond 13 that is a siloxane bond, and the other surface of the organic thin film 1C is bonded to the substrate 12 via a chemical bond 14 that is a gold-thiol bond. Has been.

In the third embodiment, since the organic molecules forming the first organic molecular skeleton layer 2 also have a skeleton for forming the network layer 3 and the second organic molecular skeleton 4, the material used is The number of manufacturing steps can be reduced.
In the third embodiment, the network layer 3 uses a bond by a crosslinking reaction of a diacetylene group, and the crosslinking reaction is performed by light irradiation. Similarly to the case of the siloxane bond in the first and second aspects described above, the network due to the crosslinking of the diacetylene group can suitably suppress the passage of gas molecules through the network layer 3 and the organic thin film 1A.

Furthermore, in the 3rd aspect, since the base materials 11 and 13 and the organic thin film 1C are couple | bonded by the chemical bond, the adhesiveness of the base materials 11 and 13 and the organic thin film 1C is high. In addition, as the first organic molecular skeleton layer 2 and the second organic molecular skeleton layer 4, by using a linear alkane having a long total number of carbon atoms of 22 as in the formula (4) in FIG. The one organic molecular skeleton layer 2 and the second organic molecular skeleton layer 4 can be arranged in a substantially vertical direction with respect to the base materials 11 and 13, and the chemical bonds 12 and 14 are reliably formed. This effect can also be obtained when the first organic molecular skeleton layer 2, the network layer 3, and the second organic molecular skeleton layer 4 are formed of one molecule as in this embodiment.
The film 20C of the third aspect can be manufactured as follows, for example. Moreover, the schematic process drawing of a manufacturing method is shown in FIG.

1. Preparatory process of the base material 11 The PVA film of the base material 11 is prepared, and the film surface is washed by UV / O ₃ treatment.
2. Monomolecular film forming step A 1 mM toluene solution of the molecule represented by the formula (4) in FIG. 9 is prepared, and the base material 11 is immersed in the solution, whereby the hydroxyl group of PVA and the formula ( A siloxane bond is formed by reacting with the silane coupling site of the molecule represented by 4). As the silane coupling site of the molecule represented by the formula (4), trihalosilane (halogen atoms include chlorine, bromine and iodine), trimethoxysilane and triethoxysilane are preferable. Moreover, the molecule | numerator which has a diacetylene part in the center part of C22 long-chain alkyl like Formula (4) can arrange the molecule | numerator of Formula (4) with high density in the substantially perpendicular direction. This is possible, and the cross-linking reaction between adjacent diacetylene sites in the surface is likely to proceed, so that a network of acetylene-ethylene bonds develops. Moreover, since the terminal thiol group is steadily exposed on the surface of the film because it can be arranged in a substantially vertical direction, chemical bonds can be formed in many places with the base material 2 on the upper side, and the adhesiveness is improved. .
Note that the formation of the monomolecular film composed of the molecule represented by the formula (4) in FIG. 9 is carried out by XPS surface elemental analysis, and the sulfur of the thiol group of the molecule represented by the formula (4) ( This can be confirmed by identifying (S2s orbit). In addition, it is possible to identify molecules on the film surface by using solid-state NMR or FT-IR. In particular, by performing polarized light FT-IR measurement and comparing the absorption intensity of the alkyl chain or diacetylene moiety in the s wave and p wave, the molecule represented by the formula (4) in FIG. 9 is substantially perpendicular to the substrate. It can be seen that they are arranged in the direction. Specifically, if the molecules are oriented in a direction perpendicular to the base material, the peak intensity of CH ₂ expansion / contraction is observed to be larger when the s wave is incident than when the p wave is incident.
3. Step of forming network layer 3 The film on which the layer composed of the molecule represented by formula (4) in FIG. 9 is formed is irradiated with ultraviolet light of 254 nm with a commercially available UV lamp for about 2 minutes. The diacetylene moiety is crosslinked to form an acetylene-ethylene bond. The progress of the crosslinking reaction can be judged from confirming the extension of π-conjugate due to the formation of acetylene-ethylene bond by UV-vis absorption spectrum. Specifically, the absorption intensity near 600 nm increases.
At this time, the acetylene-ethylene bond blocks or separates the gap between the organic molecular skeletons on the base material 11 side and the base material 12 side in the network layer 3, thereby suppressing the permeation of gas molecules.
4). Formation process of base material 12 By forming a thin film made of gold by vacuum deposition on the surface of the film on which the layer made of the molecule represented by formula (4) is formed, the molecule represented by formula (4) is formed. The thiol group and the gold atom form a gold-thiol bond, and the gas barrier film 20C is manufactured.

The gas barrier film 20C obtained as described above has a structure represented by the above formula, and can exhibit a good gas barrier ability by including the network layer 3 bonded in the in-plane direction. The gas barrier ability can be measured for oxygen and moisture permeability by a known method using, for example, a known gas permeability measuring device as shown in Patent Document 1.
Further, the gas barrier film obtained as described above has the structure shown in the above formula, and has a strength as a film by being bonded to the base materials 11 and 12 by a chemical bond. The thin film 1C is difficult to peel off. The adhesiveness between the base materials 11 and 12 and the organic thin film 1C can be confirmed by a peel test using a known cellophane tape.

FIG. 10A shows the chemical structure of the molecules constituting the connection layer of the third embodiment. Moreover, the chemical structure of the molecule | numerator which comprises the network layer before performing bridge | crosslinking of a 3rd aspect is shown to Fig.11 (a). For these molecules, the most stable structure is calculated by quantum chemical calculation, and schematic diagrams when the molecules are arranged on the substrate are shown in FIGS. 10 (b), 10 (c), 11 (b) and 11 (c). Show. FIGS. 10B and 10C show structures after crosslinking, and FIGS. 11B and 11C show structures before crosslinking. 10 (b) and 10 (b) are structures when projected from the horizontal direction on the base material, and FIGS. 10 (c) and 11 (c) are views from the vertical direction with respect to the base material. This is the structure when projected. The calculation was performed at the Gaussian 09 B3LYP 6-31G (d, p) level.
As shown in FIGS. 10 to 11, when the molecules are cross-linked, it can be seen that the molecules are largely bent and a stone wall structure is formed. In addition, before the cross-linking, a gap penetrates between the base material 11 and the base material 12 as shown in FIG. 11B, but after the cross-linking, as shown in FIG. It can be seen that this gap and the gap on the substrate 12 side are blocked. Similarly, when projected from the vertical direction with respect to the base materials 11 and 12 (comparison between FIG. 10 (c) and FIG. 11 (c)), in FIG. Considering the diameter of oxygen molecules and water molecules (0.34 nm and 0.39 nm, respectively), it is difficult to suppress the transmission, but as shown in FIG. If so, chemical bonds exist and can fill the gaps between molecules. That is, it can be seen that by cross-linking between molecules, the cross-linked chemical bond serves as a bottleneck for gas permeation and can suppress gas permeation.

[Fourth Aspect / Film]
A specific example of the film of the fourth aspect will be described with reference to the schematic view of FIG.
A film 20D of the fourth embodiment shown in FIG. 12 has a first organic molecular skeleton layer 2 made of linear alkane (octadecane), a network layer 3 having a polyacrylic acid skeleton, and a second layer made of linear alkane (octadecane). The organic thin film 1D of the present invention comprising the organic molecular skeleton layer 4, the second network layer 3 ′, and the third organic molecular skeleton layer 6 made of linear alkane (octadecane), and the substrate 11 made of PEN, It is a film provided with the base material 12 which consists of aluminum oxide. One surface of the organic thin film 1D is bonded to the substrate 11 via a chemical bond 13 that is a siloxane bond, and the other surface of the organic thin film 1D is bonded to the substrate 12 via a chemical bond 14 that is a phosphonate bond. Has been.

In the fourth embodiment, the polymer (polyacrylic acid) represented by the formula (5) in FIG. 13 is used for the network layer 3 and the second network layer 3 ′, so that A network layer in which the main chain is oriented is formed. Since the long main chain of the polymer can block the gap between the molecular skeletons in the first organic molecular skeleton layer and the second organic molecular skeleton layer, the gas permeation between the base material 11 and the base material 12 is performed. Can be suppressed and blocked. Moreover, since the position of the functional group of the side chain can be determined by using the polymer, the bonding position of each organic molecular skeleton and the network layer 3 or the second network layer 3 ′ (in this embodiment, the above formula The bonding position between the hydroxyl group obtained by oxidation of ethylene of the molecule represented by (1) and the carboxylic acid of polyacrylic acid represented by formula (5) in FIG. 13 or the formula (6 in FIG. 13) ) And the binding position of the acrylic acid carboxylic acid represented by the formula (5) in FIG. For example, when the monomer represented by the formula (5) in FIG. 13 is used, the organic molecular skeleton on the substrate 12 side is shifted laterally because there is no bonding point immediately above the organic molecular skeleton on the substrate 11 side. Join in position (see FIG. 13). Therefore, the stone wall structure can be easily formed, and the path through which gas molecules pass through the organic thin film 1D is complicated, and the distance becomes long, so that the gas barrier performance is improved.
The film 20D of the fourth aspect can be manufactured as follows, for example. Moreover, the schematic process drawing of a manufacturing method is shown in FIG.

1. Preparation of Substrate A monomolecular film having a hydroxyl group on the surface is obtained by performing steps 1 to 3 of the first aspect.
2. Network layer forming step The film of step 1 is immersed in a methylene chloride solution of polyacrylic acid, and further, EDC (1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride) and NHS (N-hydroxysuccinimide) Is added to form an active ester of carboxylic acid of polyacrylic acid to form an ester bond with a hydroxyl group on the surface of the substrate. To remove excess polyacrylic acid, the membrane is washed with methylene chloride and water.
3. Formation of second layer of monomolecular film The film of step 2 is immersed in a methylene chloride solution of the molecule represented by the formula (6), and EDC and NHS are added to the solution, whereby the carboxylic acid and the formula on the surface of the crosslinked layer are added. An amide bond is formed with the amino group of the molecule represented by (6).
4). Formation of second network layer and monomolecular film (third layer) The second network layer and the monomolecular film are laminated in the same manner as in Step 2 and Step 3 above. In addition, it can be judged from FT-IR and XPS that each layer was formed similarly to the 1st aspect.
5. Formation of Substrate 12 By performing Steps 6 and 7 of the first embodiment, a phosphonic acid site is exposed on the surface of the monomolecular film, and further, between the aluminum oxide of the substrate 12 and the phosphonic acid on the film surface. By forming a phosphate ester bond, the gas barrier film 20D can be manufactured.
The network layer of this embodiment has a feature that a polymer having a long main chain synthesized in advance can be arranged in the in-plane direction, and is easy to form a stone wall structure. The gas barrier film 20B of the second embodiment Similarly, it exhibits high gas barrier properties.

[Fifth Aspect / Film]
A specific example of the film of the fifth aspect will be described with reference to the schematic diagram of FIG.
A film 20E of the fifth embodiment shown in FIG. 14 includes a first organic molecular skeleton layer 2 made of linear alkane (decane), a network layer 3 made of 1,5-substituted naphthalene, and a linear alkane (decane). It is a film comprising the organic thin film 1D of the present invention comprising the third organic molecular skeleton layer 6 comprising the second organic molecular skeleton layer 4 comprising the substrate 11 comprising PEN and the substrate 12 comprising aluminum oxide. . One surface of the organic thin film 1E is bonded to the substrate 11 through a chemical bond 13 that is a siloxane bond, and the other surface of the organic thin film 1E is bonded to the substrate 12 through a chemical bond 14 that is a phosphonate bond. Has been. The first organic molecular skeleton layer 2 and the network layer 3 include the NH ₂ group of the molecule represented by the chemical formula (7), which is a molecule for forming the first organic molecular skeleton layer 2, and the network layer 3. They are bound by an imine bond formed by an aldehyde group of a molecule represented by the chemical formula (8) which is a molecule for forming. In addition, the network layer 3 and the second organic molecular skeleton layer 4 are an NH ₂ group of a molecule represented by the chemical formula (9), which is a molecule for forming the second organic molecular skeleton layer 4, and a network layer. Are linked by an imine bond formed by the aldehyde group of the molecule to form 3.

In the fifth embodiment, naphthalene substituted at the 1,5-positions is used as the network layer 3. By having an aromatic rigid skeleton such as naphthalene and a functional group at an appropriate position, the skeleton can be oriented in the in-plane direction (horizontal with the substrate). This shows the same orientation not only in 1,5-substituted naphthalene but also in 1,4-position and 1,2-, 5-substituted naphthalene. In addition, the substituted naphthalene oriented in the in-plane direction in this way makes the distance between the molecular skeletons constituting the network layer very narrow, which acts as a bottleneck when gas molecules try to pass through and improves the gas barrier ability To do.
In the fifth aspect, the molecules forming the first organic molecular skeleton layer 2, the molecules forming the network layer 3, and the molecules forming the second organic molecular skeleton layer 4 are stacked in this order. Thus, the monomolecular film on the substrate 11 side can be densely formed without being affected by the steric hindrance of the molecules forming the network layer 3 (molecules represented by the chemical formula (8) in FIG. 15). . Therefore, also in the first organic molecular skeleton layer 2, a gap between molecules can be made very narrow, and the gas barrier ability is further improved.
The film 20E of the fifth aspect can be manufactured as follows, for example. Moreover, the schematic process drawing of a manufacturing method is shown in FIG.

1. Preparation of substrate 11 and monomolecular film formation step A monomolecular film is formed using the molecule represented by formula (7) in Fig. 15 by the same procedure as steps 1 and 2 of the first embodiment.
2. Formation of a horizontally arranged molecular layer (second layer) A 1 mM ethanol solution of the molecule represented by the formula (8) in FIG. 15 is prepared, and the film of step 1 is immersed in the solution, thereby An imine bond is formed between the amino group on the surface of the material 11 and the aldehyde group of the molecule represented by the formula (8).
3. Formation of monomolecular film (third layer) By preparing a 1 mM ethanol solution of the molecule represented by formula (9) in FIG. 15 and immersing the film of step 2 in the solution, formula (8) An imine bond is formed between the aldehyde group of the molecule represented and the terminal amino group of the molecule represented by formula (9).
4). Formation of the base material 2 By sputtering aluminum oxide of the base material 12 on the surface of the monomolecular film of the molecule represented by the formula (9), a phosphate ester bond is formed with the phosphonic acid on the film surface. The gas barrier film 20E can be manufactured.

  In this embodiment, when the binding sites (hydroxyl groups) of the base material 11 are sparse or the molecular skeleton is bulky, the molecular density of the first layer is low, and the gap between the molecules is large. However, by stacking horizontally aligned molecules (naphthalene), it is possible to create a region where the gap between naphthalene molecules is smaller than the size of a gas molecule alone or a collection of multiple aggregates (approximately 0.6 nm). And the gap can be covered (the area of the gap can be reduced). As a result, the naphthalene site becomes a gas permeation bottleneck between the base material 11 and the base material 12, thereby improving the gas barrier ability.

[Sixth aspect / display device]
A specific example of the display device of the sixth aspect will be described with reference to the schematic diagram of FIG.
In the display device 40A of the sixth embodiment shown in FIG. 16, an organic transistor 42 and an organic EL element 43 electrically connected to the organic transistor 42 are formed on a transparent substrate 41. The transparent substrate 41, the organic transistor 42 and the organic EL element 43 are covered with a sealing body 44 made of PVA resin, and the organic thin film 1B described in the second embodiment and the base material 45 made of aluminum oxide are formed on the sealing body 44. .
The organic transistor 42 includes a gate electrode 30, a gate insulating layer 31, a source electrode 32, a drain electrode 33, and an organic semiconductor layer 34. The organic EL element 43 is a top emission type and includes a pixel electrode 35, a light emitting layer 36 and a counter electrode 37.

  The display device 40A according to the sixth aspect can be manufactured as shown in FIG. First, (a) an organic transistor 42 and an organic EL element 43 are formed on a transparent substrate 41, and (b) a sealing body 44 is obtained by spin-coating a solution of PVA resin. Thereafter, (c) the organic thin film 1B is manufactured on the sealing body 44 in the same manner as in the second embodiment. The organic thin film 1B is bonded to the hydroxyl group on the upper surface of the PVA resin layer that is the sealing body 44 by a chemical bond. Subsequently, (d) It can manufacture by forming the base material 45 which consists of aluminum oxide similarly to a 2nd aspect.

The display device 40A according to the sixth aspect has a high gas barrier ability and a high adhesion property. By applying the gas barrier film according to the second aspect (the organic thin film 1B having the gas barrier ability), oxygen and Since intrusion of water is suppressed, a display device with a long life can be obtained.
Moreover, since the circumference | surroundings of an organic transistor and an organic EL element are covered with the gas barrier film, permeation | transmission of gas can be prevented more suitably.
When a gas barrier film is applied to a display device that transmits light, an optical design is usually required in consideration of the refractive index and light transmittance of the gas barrier film, adhesive layer, etc. Since the organic thin film has a thin thickness of about several nanometers, the refractive index and transmittance of the organic thin film can be virtually ignored, and the optical design becomes easy.

[Seventh aspect / display device]
A specific example of the display device of the seventh aspect will be described with reference to the schematic diagram of FIG.
In the display device 40B of the seventh aspect shown in FIG. 18, an organic transistor 42 and an organic EL element 43 electrically connected to the organic transistor 42 are formed on a transparent substrate 41. A gas barrier film 20 </ b> B of the second aspect including the material 11, the organic thin film 1 </ b> B, and the base material 12 is laminated. The gas barrier film 20B is the same as described above. Nitrogen gas is sealed between the gas barrier film 20B and the substrate 41, the organic transistor 42, and the organic EL 43. The organic transistor 42 and the organic EL element 43 are the same as in the sixth embodiment.

  The display device 40B of the seventh aspect can be manufactured as shown in FIG. First, (a) an organic transistor 42 and an organic EL element 43 are formed on a transparent substrate 41, and (b) a gas barrier film 20B manufactured in the same manner as in the second embodiment is laminated, and the internal space is filled with nitrogen gas By doing so, it can be manufactured.

Similarly to the display device 40B of the sixth aspect, the display device 40B of the seventh aspect is applied to the organic EL and the organic transistor by applying the gas barrier film of the second aspect having high gas barrier ability and high adhesiveness. Since the intrusion of oxygen and water is suppressed, a display device with a long life can be obtained.
Moreover, since the display device 40B according to the seventh aspect is merely bonded to the gas barrier film 20B according to the second aspect, the gas barrier property can be achieved by a simple process.

  The organic thin film of this invention can be utilized suitably in the manufacture field | area of an organic device etc. in which high gas barrier capability is requested | required.

DESCRIPTION OF SYMBOLS 1, 1A, 1B, 1C, 1D, 1E ... Organic thin film 2 ... First organic molecular skeleton layer 3 ... Network layer 3 '... Second network layer 4 ... Second organic molecular skeleton layer 6 ... Third organic Molecular skeleton layers 11, 12 ... base materials 13, 14 ... chemical bonds 20A, 20B, 20C, 20D, 20E ... film 30 ... gate electrode 31 ... gate insulating layer 32 ... source electrode 33 ... drain electrode 34 ... organic semiconductor layer 35 ... Pixel electrode 36 ... Luminescent layer 37 ... Counter electrode 40A, 40B ... Display element 41 ... Transparent substrate 42 ... Organic transistor 43 ... Organic EL element 44 ... Sealing body 45 ... Base material

Claims (12)

An organic thin film having at least a first organic molecular skeleton layer, a network layer laminated on the first organic molecular skeleton layer, and a second organic molecular skeleton layer laminated on the network layer. And
The organic molecular skeleton constituting the network layer is bonded in the in-plane direction, or
The major axis of the organic molecular skeleton constituting the network layer is oriented in the in-plane direction, and the distance between the in-plane directions of the organic molecular skeleton constituting the network layer in the in-plane direction is the first organic molecule. An organic thin film characterized in that it is smaller than the distance between the skeleton and the second organic molecular skeleton in the in-plane direction.   The organic thin film according to claim 1, wherein the first organic molecular skeleton and the second organic molecular skeleton are combined with an organic molecular skeleton constituting the network layer by a chemical bond. Furthermore, the second network layer laminated on the second organic molecular skeleton layer, and a third organic molecular skeleton layer laminated on the second network layer,
The organic molecular skeleton constituting the second network layer is bonded in the in-plane direction, or
The major axis of the organic molecular skeleton constituting the second network layer is oriented in the in-plane direction, and the in-plane direction spacing of the organic molecular skeleton constituting the second network layer is in the in-plane direction. 3. The organic thin film according to claim 1, wherein the organic thin film is smaller than a distance in an in-plane direction between the second organic molecular skeleton and the third organic molecular skeleton.   4. At least one of the first organic molecular skeleton layer and the second organic molecular skeleton layer is a monomolecular layer in which single organic molecules are formed side by side. Organic thin film as described in 2.   The organic thin film according to any one of claims 1 to 4, wherein the first organic molecular skeleton and the second organic molecular skeleton include a linear alkane skeleton. The first organic molecular skeleton and the second organic molecular skeleton are linear alkane skeletons;
The organic thin film according to claim 5, wherein the organic molecular skeleton constituting the network layer is a naphthalene skeleton. The first organic molecular skeleton and the second organic molecular skeleton are linear alkane skeletons;
The organic thin film according to claim 5 or 6, wherein the network layer is bonded by a siloxane bond, bonded by a diacetylene group crosslinking reaction, or has a polyacrylic acid skeleton.   A gas barrier film comprising at least a base material and the organic thin film according to any one of claims 1 to 7.   The adhesive film which consists of an organic thin film as described in any one of Claims 1-7 sandwiched by the at least 2 base material and connected with the atom of the surface of this base material by a chemical bond. A substrate, a transistor provided on the substrate, a liquid crystal, an organic electroluminescence or electrophoretic pixel electrically connected to the transistor, a sealing body that seals the transistor and the pixel, and In a display device comprising a base material that covers the surface of a sealing body,
The said sealing body and the said base material are bonded together through the organic thin film as described in any one of Claims 1-7, The display apparatus characterized by the above-mentioned.   A film comprising the organic thin film according to any one of claims 1 to 7 and a base material, wherein an organic molecular skeleton on the surface of the organic thin film and atoms on the base material surface are bonded by a chemical bond. A substrate, a transistor provided on the substrate, a liquid crystal, an organic electroluminescence or electrophoretic pixel electrically connected to the transistor, and a gas barrier film provided on the substrate, the transistor, and the pixel In a display device comprising:
The said gas barrier film consists of a film of Claim 11, The display apparatus characterized by the above-mentioned.

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