WO2022255179A1 - 複合膜の製造方法、及び有機無機ハイブリッド膜の製造方法 - Google Patents
複合膜の製造方法、及び有機無機ハイブリッド膜の製造方法 Download PDFInfo
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- WO2022255179A1 WO2022255179A1 PCT/JP2022/021334 JP2022021334W WO2022255179A1 WO 2022255179 A1 WO2022255179 A1 WO 2022255179A1 JP 2022021334 W JP2022021334 W JP 2022021334W WO 2022255179 A1 WO2022255179 A1 WO 2022255179A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Definitions
- the present invention relates to a method for manufacturing a composite membrane and a method for manufacturing an organic-inorganic hybrid membrane.
- the applicant proposed forming an organic-inorganic hybrid film of cerium oxide and an organic fluorine compound on the surface of the transparent resin laminate. More specifically, the present applicant uses a sputtering apparatus capable of performing bipolar sputtering as a method for producing the organic-inorganic hybrid film, and uses an organic material target and an inorganic material target. And proposed a manufacturing method using a target of a mixture of an organic material and an inorganic material (see Patent Document 3).
- Patent Document 3 proposes a manufacturing method using a target of a mixture of an organic material and an inorganic material.
- An object of the present invention is to provide a novel method for producing a composite membrane.
- a further object of the present invention is to provide a novel method for producing an organic-inorganic hybrid film.
- a method of manufacturing a composite membrane comprising: using a sputtering device, (A) a solid substance target under standard conditions (temperature 25° C., pressure 100 KPa), and (B) a substance gas capable of preparing a mixed gas with a sputtering gas, (1) A step of mounting the (A) target on a target installation jig of the sputtering apparatus; (2) reducing the pressure in the sputtering chamber of the sputtering apparatus to a first predetermined pressure; (3) Introducing a mixture of the sputtering gas and the gas (B) into the sputtering chamber of the sputtering apparatus so that the pressure in the sputtering chamber reaches a second predetermined pressure that is equal to or higher than the first predetermined pressure.
- the above production method including the step of forming the composite film on the surface of the substrate by applying power to the (A) target and sputtering.
- the mixing ratio of the mixed gas is 60/40 to 99.999/0.001, [1 ] or the production method according to [2]. [4].
- the gas of the organic compound is a compound having a structure in which one or more hydrogen atoms of saturated hydrocarbon are substituted with fluorine atoms and is gaseous under standard conditions (temperature 25 ° C., pressure 100 KPa), and 1 selected from the group consisting of compounds having a structure in which one or more hydrogen atoms of unsaturated hydrocarbons are substituted with fluorine atoms and which are gaseous under standard conditions (temperature 25° C., pressure 100 KPa)
- the production method according to item [4] which contains a gas of at least one kind of compound. [6].
- the manufacturing method according to any one of items [1] to [5], wherein the target (A) is an inorganic target. [7].
- the sputtering apparatus is a roll-to-roll type sputtering apparatus; The mixing ratio of the mixed gas (volume of the sputtering gas/volume of the (B) gas: converted to standard conditions (0° C.
- the (B) gas comprises an organic compound gas;
- the gas of the organic compound is a compound having a structure in which one or more hydrogen atoms of saturated hydrocarbon are substituted with fluorine atoms and is gaseous under standard conditions (temperature 25 ° C., pressure 100 KPa), and 1 selected from the group consisting of compounds having a structure in which one or more hydrogen atoms of unsaturated hydrocarbons are substituted with fluorine atoms and which are gaseous under standard conditions (temperature 25° C., pressure 100 KPa) containing gases of more than one species;
- the target is an inorganic substance target;
- the inorganic material target comprises an inorganic material having a bandgap of 2.6-3.7 eV;
- the sputtering apparatus is a roll-to-roll type sputtering apparatus; The mixing ratio of the mixed gas (volume of the sputtering gas/volume of the (B) gas: converted to standard conditions (0° C.
- the (B) gas comprises an organic compound gas
- the gas of the organic compound is a compound having a structure in which one or more hydrogen atoms of saturated hydrocarbon are substituted with fluorine atoms and is gaseous under standard conditions (temperature 25 ° C., pressure 100 KPa), and 1 selected from the group consisting of compounds having a structure in which one or more hydrogen atoms of unsaturated hydrocarbons are substituted with fluorine atoms and which are gaseous under standard conditions (temperature 25° C., pressure 100 KPa) containing gases of more than one species;
- the target is an organic compound target; The manufacturing method according to item [1], wherein the target of the organic compound contains a silicone resin.
- a method for producing an organic-inorganic hybrid film comprising: using a sputtering device, Using an inorganic target and an organic compound gas, (1) a step of mounting the target of the inorganic material on a target installation jig of the sputtering apparatus; (2) reducing the pressure in the sputtering chamber of the sputtering apparatus to a first predetermined pressure; (3) introducing a mixed gas of the sputtering gas and the organic compound gas into the sputtering chamber of the sputtering apparatus so that the pressure in the sputtering chamber reaches a second predetermined pressure that is equal to or higher than the first predetermined pressure; process; and (4)
- the above manufacturing method including the step of forming the organic-inorganic hybrid film on the surface of the base material by applying electric power to the target of the inorganic substance and sputtering the target.
- the gas of the organic compound is a compound having a structure in which one or more hydrogen atoms of saturated hydrocarbon are substituted with fluorine atoms and is gaseous under standard conditions (temperature 25 ° C., pressure 100 KPa), and 1 selected from the group consisting of compounds having a structure in which one or more hydrogen atoms of unsaturated hydrocarbons are substituted with fluorine atoms and which are gaseous under standard conditions (temperature 25° C., pressure 100 KPa)
- the present method is suitable as a method for producing a composite membrane, particularly as a production method for forming a composite membrane with high productivity by a roll-to-roll method.
- the bipolar sputtering apparatus has complicated specifications, and as a result, handling and setting of the apparatus are severe.
- the methods and conditions are greatly different, and it is difficult to industrially prepare a target of a mixture of an organic material and an inorganic material.
- the present method is suitable as a method for producing an organic-inorganic hybrid film, particularly as a production method for forming an organic-inorganic hybrid film with high productivity by a roll-to-roll method.
- FIG. 1 is a conceptual diagram showing an example of a roll-to-roll type sputtering apparatus.
- FIG. 2 is a photograph showing an example of a roll-to-roll type sputtering apparatus provided with an anti-adhesion plate.
- FIG. 3 is a conceptual diagram showing an example of a batch type sputtering apparatus.
- FIG. 4 is a spectrum obtained by XPS analysis of the sputtered film (organic-inorganic hybrid film) of Example 1 in the energy region attributed to the fluorine atom 1s orbital.
- FIG. 5 is a spectrum obtained by XPS analysis of the sputtered film (organic-inorganic hybrid film) of Example 1 in the energy range of ⁇ 10 to 1350 eV.
- FIG. 4 is a spectrum obtained by XPS analysis of the sputtered film (organic-inorganic hybrid film) of Example 1 in the energy range of ⁇ 10 to 1350 eV.
- FIG. 6 is a spectrum obtained by XPS analysis of the sputtered film (organic-inorganic hybrid film) of Example 2 for the energy region attributed to the fluorine atom 1s orbital.
- FIG. 7 is a spectrum obtained by XPS analysis of the sputtered film (organic-inorganic hybrid film) of Example 2 in the energy range of ⁇ 10 to 1350 eV.
- FIG. 8 is a spectrum obtained by XPS analysis of the sputtered film (organic-inorganic hybrid film) of Example 3 for the energy region attributed to the fluorine atom 1s orbital.
- FIG. 7 is a spectrum obtained by XPS analysis of the sputtered film (organic-inorganic hybrid film) of Example 2 in the energy range of ⁇ 10 to 1350 eV.
- FIG. 8 is a spectrum obtained by XPS analysis of the sputtered film (organic-inorganic hybrid film) of Example 3 for the energy region attributed to the fluorine atom 1s
- FIG. 9 is a spectrum obtained by XPS analysis of the sputtered film (organic-inorganic hybrid film) of Example 3 in the energy range of ⁇ 10 to 1350 eV.
- FIG. 10 is a spectrum obtained by XPS analysis of the sputtered film (organic-inorganic hybrid film) of Example 4 in the energy region attributed to the fluorine atom 1s orbital.
- FIG. 11 is a spectrum obtained by XPS analysis of the sputtered film (organic-inorganic hybrid film) of Example 4 in the energy range of ⁇ 10 to 1350 eV.
- inorganic substance is used as a term including mixtures containing two or more inorganic substances.
- organic compound is used as a term that also includes mixtures containing two or more organic compounds.
- resin is used as a term including resin mixtures containing two or more resins and resin compositions containing components other than resins.
- film is used interchangeably or interchangeably with “sheet”.
- sheet As used herein, the terms “film” and “sheet” are used for those that can be industrially wound into rolls.
- plate is used for those that cannot be industrially wound into rolls.
- laminating a certain layer and another layer in order means directly laminating those layers, and interposing one or more layers such as an anchor coat between those layers. and lamination.
- the term "greater than or equal to” related to a numerical range is used to mean a certain numerical value or more than a certain numerical value. For example, 20% or more means 20% or more than 20%.
- the term “up to” relating to a numerical range is used to mean a certain numerical value or less than a certain numerical value. For example, 20% or less means 20% or less than 20%.
- the symbol “ ⁇ ” relating to numerical ranges is used to mean a certain numerical value, greater than a certain numerical value and less than another numerical value, or other numerical value.
- another certain numerical value is assumed to be a larger numerical value than the certain numerical value. For example, 10-90% means 10%, greater than 10% and less than 90%, or 90%.
- the upper limit and the lower limit of the numerical range can be arbitrarily combined, and embodiments in which they are arbitrarily combined can be read.
- the numerical range of a certain characteristic "usually 10% or more, preferably 20% or more. On the other hand, it is usually 40% or less, preferably 30% or less.” ⁇ 30%.”, it should be read that the numerical range for that certain property is 10-40%, 20-30%, 10-30%, or 20-40% in one embodiment. do.
- composite film means a film containing atoms derived from each of two or more substances.
- organic-inorganic hybrid film refers to a film containing atoms (which may constitute a molecule) derived from an inorganic substance and atoms (which may constitute a molecule) derived from an organic compound. means.
- the method for producing the composite membrane of the present invention comprises: using a sputtering device, (A) using a substance gas capable of preparing a mixed gas of a solid substance target under standard conditions (temperature 25° C., pressure 100 KPa) and (B) sputtering gas, (1) A step of mounting the (A) target on a target installation jig of the sputtering apparatus; (2) reducing the pressure in the sputtering chamber of the sputtering apparatus to a first predetermined pressure; (3) Introducing a mixture of the sputtering gas and the gas (B) into the sputtering chamber of the sputtering apparatus so that the pressure in the sputtering chamber reaches a second predetermined pressure that is equal to or higher than the first predetermined pressure. process; and (4) applying power to the (A) target and sputtering to form the composite film on the surface of the substrate;
- the composite film formed by the composite film manufacturing method of the present invention includes (A) atoms derived from a solid substance in the standard state (temperature 25 ° C., pressure 100 KPa), and (B) a mixed gas with the sputtering gas including atoms from substances that can prepare
- the composite membrane formed by the method for producing a composite membrane of the present invention includes (A) atoms derived from a solid substance in the standard state (temperature 25 ° C., pressure 100 KPa), and the above ( B) contains atoms derived from a substance capable of preparing a mixed gas with the sputtering gas, and is modified by one of the substances (usually, it may be a substance capable of preparing a mixed gas with the above (B) sputtering gas); It may contain the other substance (usually, it may be a solid substance under the above (A) standard conditions (temperature 25° C., pressure 100 KPa)).
- the method for producing the composite membrane of the present invention will be described mainly by taking the case of the method for producing an organic-inorganic hybrid membrane as an example.
- the “organic-inorganic hybrid film” is referred to as the “composite film”
- the “inorganic compound target” is referred to as “(A) standard conditions (temperature 25 ° C., pressure 100 KPa). If the composite film manufacturing method of the present invention is carried out by appropriately reading "solid substance target” and "organic compound gas” as "(B) substance gas capable of preparing a mixed gas with sputtering gas”. It goes without saying that it is good.
- the method of manufacturing the composite film of the present invention uses a sputtering apparatus.
- the method for producing an organic-inorganic hybrid film of the present invention uses a sputtering apparatus.
- the sputtering apparatus is not particularly limited, and a known sputtering apparatus can be used.
- As the sputtering apparatus from the viewpoint of forming an organic-inorganic hybrid film with good productivity, a film substrate is fed out from a film roll, an organic-inorganic hybrid film is formed on the surface of the film substrate, and then wound as a film roll.
- a sputtering apparatus having a mechanism for removing the film hereinafter sometimes referred to as "roll-to-roll type sputtering apparatus" is preferable.
- FIG. 1 is a conceptual diagram showing an example of a roll-to-roll type sputtering apparatus.
- the apparatus of FIG. 1 comprises a payout roll 2, a transfer roll 3, a sputter roll 4, a transfer roll 3' and a take-up roll 5 in a sputtering chamber 1.
- the film substrate 10 is fed out from the film roll 12, an organic-inorganic hybrid film (not shown) is formed on the surface of the film substrate 10, and then the organic-inorganic hybrid film is formed on the surface of the film substrate 10.
- a laminate 11 having a membrane (not shown) is adapted to be wound up as a film roll 12'.
- a device having two or more sputtering rolls may be used as the roll-to-roll type sputtering device. It becomes possible to easily install two or more target installation jigs, thereby increasing the deposition rate and line speed (productivity) by using two or more targets.
- the first sputtering roll after forming an anchor film (a film that functions as an anchor for increasing the interlayer adhesion strength between the film substrate and the organic-inorganic hybrid film) on the surface of the film substrate, two An organic-inorganic hybrid film can be formed on the surface of the anchor film in the subsequent sputtering rolls. This makes it possible to obtain a laminate having the film substrate, the anchor film, and the organic-inorganic hybrid film in one pass.
- the sputtering chamber 1 has a sputtering gas inlet 6 so that gas (sputtering gas and gas mixed with the sputtering gas) can be introduced into the sputtering chamber 1 through the sputtering gas inlet 6 .
- the sputtering chamber 1 has an exhaust port 7, and an exhaust device (not shown) is used to evacuate from the exhaust port 7 so that a predetermined pressure can be maintained.
- the exhaust device is not particularly limited as long as it has the ability to maintain the predetermined pressure.
- Examples of the evacuation device include positive displacement vacuum pumps such as oil rotary pumps, momentum transfer vacuum pumps such as turbomolecular pumps, gas reservoir vacuum pumps such as cryopumps, and combinations thereof. .
- the apparatus in FIG. 1 has two target installation jigs 8, 8', and can mount one target each (total two) targets 9, 9'.
- the targets 9 and 9' attached to the target installation jigs 8 and 8' are equipped with separate impedance matching devices (not shown) and high-frequency power sources so that the film formation conditions can be appropriately adjusted. (not shown) are connected. Thereby, the power supplied to the targets 9 and 9' can be individually controlled.
- a flow path for a medium such as water is provided so that the temperature of the targets 9, 9' can be controlled to a predetermined temperature.
- the targets 9, 9' attached to the target installation jigs 8, 8' are arranged to face the sputtering roll 4.
- the distance between the target 9 and the sputtering roll 4 is not particularly limited, but it is usually about 1 to 20 cm, preferably 3 to 15 cm, more preferably about 5 to 12 cm. .
- a target of a substance that is solid under standard conditions The method for producing a composite membrane of the present invention uses (A) a target that is a substance that is solid under standard conditions (temperature: 25°C, pressure: 100 KPa). That is, the composite membrane produced by the method for producing a composite membrane of the present invention contains atoms derived from a solid substance under the above (A) standard conditions (temperature of 25° C., pressure of 100 KPa).
- the substance (A) is a substance that can stably maintain a solid state under standard conditions (temperature of 25 ° C., pressure of 100 KPa), preferably standard conditions (temperature of 25 ° C., pressure of 100 KPa), and the above composite There is no particular limitation except that the material can stably maintain a solid state at the pressure and temperature in each step of film formation.
- the substance (A) may be an inorganic substance or an organic compound.
- organic compounds include silicone resins.
- the silicone resin is a polymer compound having a siloxane bond (Si--O--Si) as a main skeleton.
- the silicone resin is not particularly limited as long as it has the above structure, and examples thereof include polydimethylsiloxane, polydiethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, and modified products thereof. One or a mixture of two or more of these can be used as the silicone resin.
- the substance (A) is a substance that can stably maintain a solid state under standard conditions (temperature of 25° C., pressure of 100 KPa), preferably standard conditions (temperature of 25° C., pressure of 100 KPa), and forms the composite membrane.
- standard conditions temperature of 25° C., pressure of 100 KPa
- standard conditions temperature of 25° C., pressure of 100 KPa
- it can be appropriately selected from among substances that can stably maintain a solid state at the pressure and temperature in each step.
- the above (A) substance is molded by a known method and the molded body is used as a target.
- the substance (A) is an inorganic substance
- examples of the method include sintering.
- examples of the method include injection molding and cast solidification.
- the shape of the target of the substance (A) can be appropriately selected from the viewpoint of making the film thickness of the composite film uniform, taking into account the specifications of the sputtering apparatus to be used.
- the organic-inorganic hybrid film production method of the present invention uses an inorganic target. That is, the organic-inorganic hybrid film produced by the method for producing an organic-inorganic hybrid film of the present invention contains atoms derived from the inorganic substance.
- the inorganic substance is an inorganic substance that can stably maintain a solid state under standard conditions (temperature of 25° C., pressure of 100 KPa), preferably standard conditions (temperature of 25° C., pressure of 100 KPa), and There is no particular limitation except that the inorganic substance can stably maintain a solid state at the pressure and temperature in each step of forming the hybrid film.
- the inorganic substance is an inorganic substance that can stably maintain a solid state under standard conditions (temperature 25° C., pressure 100 KPa), preferably standard conditions (temperature 25° C., pressure 100 KPa), and the organic-inorganic hybrid membrane.
- standard conditions temperature 25° C., pressure 100 KPa
- standard conditions temperature 25° C., pressure 100 KPa
- organic-inorganic hybrid membrane the organic-inorganic hybrid membrane.
- the transmittance of ultraviolet light having energy equal to or higher than the energy of the carbon-carbon bond of the organic compound (3.82 eV) is sufficient.
- the bandgap is usually 3.7 eV or less, preferably 3.6 eV or less, more preferably 3.5 eV. In the following, more preferably 3.4 eV or less, still more preferably 3.3 eV or less, and most preferably 3.25 eV or less can be mentioned.
- the inorganic substance used when trying to impart high visible light transmittance to the organic-inorganic hybrid film the viewpoint of sufficiently transmitting visible light with a wavelength of 490 nm or more (energy of visible light with a wavelength of 490 nm is 2.53 eV) Furthermore, from the viewpoint of sufficiently transmitting visible light with a wavelength of 400 nm or more (energy of visible light with a wavelength of 400 nm is 3.10 eV), the bandgap is usually 2.6 eV or more, preferably 2.7 eV or more, more preferably 2 0.8 eV or higher, more preferably 2.9 eV or higher, even more preferably 3.0 eV or higher, still more preferably 3.1 eV or higher, and most preferably 3.15 eV or higher.
- the bandgap is the energy level between the top of the highest energy band occupied by electrons and the bottom of the lowest empty band in the crystal band structure of an inorganic material.
- the bandgap is 3.7 eV or less, 3.6 eV or less, 3.5 eV or less, 3.4 eV or less, 3.3 eV or less, or 3.25 eV or less, and (in combination with any of these upper limits) a bandgap of 2.6 eV or more;2. 7 eV or more, 2.8 eV or more, 2.9 eV or more, 3.0 eV or more, 3.1 eV or more, or 3.15 eV or more), low ultraviolet transmittance and visible light transmittance. It is believed that a high quality organic-inorganic hybrid film can be formed.
- Examples of the inorganic substance used for imparting low ultraviolet transmittance and high visible light transmittance to the organic-inorganic hybrid film include cerium dioxide (3.2 eV) and cerium oxide such as dicerium trioxide; Titanium dioxide (anatase type 3.2 eV, rutile type 3.0 eV), gallium nitride (3.4 eV), zinc oxide (3.37 eV), zinc sulfide (3.6 eV), and silicon carbide (2.86 eV) I can give The numbers in parentheses are bandgaps. Among these, cerium oxides such as cerium dioxide (3.2 eV) and cerium trioxide, and anatase titanium dioxide are preferred, and cerium dioxide is more preferred.
- One or a mixture of two or more of these can be used as the inorganic substance.
- the above-mentioned inorganic substance is molded in advance by a known method such as sintering, and the molded body such as a sintered body is used as a target.
- the shape of the target of the inorganic material can be appropriately selected from the viewpoint of making the film thickness of the organic-inorganic hybrid film uniform, taking into account the specifications of the sputtering apparatus to be used. can.
- the shape of the target of the inorganic substance includes the specifications (width, diameter) of the sputtering roll arranged opposite to the target, and the target and the sputtering roll. , the width of the film substrate to be used, and the effective width of the laminate having an organic-inorganic hybrid film on the surface of the film substrate (the width of the final product of the laminate).
- the film thickness and composition of the organic-inorganic hybrid film can be appropriately selected so as to be uniform within the effective width of the body.
- the shape of the target of the inorganic substance can be appropriately selected from the viewpoint of preventing lateral fluctuations in the film thickness and the composition, and from the viewpoint of suppressing contamination of the sputtering roll.
- the shape of the inorganic substance target may be a rectangular parallelepiped.
- the horizontal length of the rectangular parallelepiped (that is, the length of the side (usually the long side) corresponding to the width direction of the sputtering roll of the vertical and horizontal surfaces of the rectangular parallelepiped target facing the sputtering roll) is the length of the organic-inorganic hybrid film.
- the length is usually equal to or greater than the effective width of the laminate, preferably equal to or greater than the width of the film substrate, and more preferably the length is equal to or greater than the effective width of the laminate. may have a length equal to or greater than the width of the film substrate plus 3 cm.
- FIG. 2 is a photograph showing an example of a roll-to-roll type sputtering apparatus provided with an anti-adhesion plate. In the apparatus shown in FIG.
- the anti-adhesion plate 13 shaped to mask the side of the sputtering roll 4 is attached to a position facing the side of the sputtering roll 4 by the anti-adhesion plate mounting jig 14 .
- the targets of the inorganic substance are the anti-adhesion plate 13, the anti-adhesion plate mounting jig 14, the anti-adhesion plate on the side opposite to the side shown in the photograph, and the anti-bonding plate mounting jig on the side opposite to the side shown in the photograph. is installed so as to face the sputtering roll 4 in the space formed by .
- the shape of the inorganic substance target is, for example, when the sputtering roll has a width of 70 cm and a diameter of 40 cm, a distance between the target and the sputtering roll of 8 cm, a width of the film substrate of 50 cm, and an effective width of the laminate of 40 cm.
- the vertical length is usually 1 to 30 cm, preferably 5 to 20 cm
- the horizontal length is usually 40 to 60 cm, preferably 53 to 58 cm
- the height is usually 0.1 to 5 cm, preferably 0.1 cm to 5 cm. It may be a rectangular parallelepiped of about 2 to 2 cm.
- a gas of a substance capable of preparing a mixed gas with a sputtering gas uses (B) a gas of a substance capable of preparing a mixed gas with a sputtering gas. That is, the composite film produced by the method for producing a composite film of the present invention contains atoms derived from a substance capable of preparing a mixed gas with the above (B) sputtering gas.
- the method for producing a composite membrane of the present invention uses a gas as one of the substances forming the composite membrane, and does not use a target. Therefore, according to the manufacturing method of the composite membrane of the present invention, the above problems are fundamentally solved.
- the (B) substance capable of preparing a mixed gas with the sputtering gas is a substance capable of preparing a mixed gas with the sputtering gas. , is not particularly limited except that it is a substance that can stably maintain a gaseous state.
- the (B) substance capable of preparing a mixed gas with the sputtering gas is not limited to a gaseous substance under standard conditions (temperature of 25° C., pressure of 100 KPa).
- the substance capable of preparing a mixed gas with the above-mentioned (B) sputtering gas is a substance that becomes a gas by heating (usually below the upper limit temperature at which the film substrate can be practically used) and/or by reducing pressure. good.
- the substance capable of preparing a mixed gas with the sputtering gas (B) is prepared by mixing the sputtering gas with the substance capable of preparing a mixed gas of the sputtering gas (B) to prepare a mixed gas of both. From the viewpoint of workability, it may preferably be a gaseous substance under standard conditions (temperature of 25° C., pressure of 100 KPa).
- the (B) substance capable of preparing a mixed gas with the sputtering gas may be an organic compound or an inorganic substance.
- the substance capable of preparing a mixed gas with the above (B) sputtering gas is selected from substances that can stably maintain a gaseous state at the pressure and temperature in each step of forming the composite film. It can be appropriately selected in consideration of the properties and functions to be imparted to the composite membrane.
- the method for producing an organic-inorganic hybrid film of the present invention uses a gas of an organic compound. That is, the organic-inorganic hybrid film produced by the method for producing an organic-inorganic hybrid film of the present invention contains atoms derived from the gas of the organic compound.
- the bipolar sputtering apparatus has complicated specifications, and as a result, Inconvenience that the handling and setting of the device becomes severe, making it difficult to industrially form an organic-inorganic hybrid film with stable quality (uniformity of film thickness, composition, etc.);
- the method and conditions suitable for target production differ greatly depending on the material, and there is the inconvenience that it is difficult to industrially prepare a target of a mixture of an organic material and an inorganic material.
- the method for producing an organic-inorganic hybrid film of the present invention uses gas as an organic compound and does not use an organic compound target (a compact as an organic compound target). Therefore, according to the method for producing an organic-inorganic hybrid film of the present invention, both of the above two problems are fundamentally resolved.
- the organic compound is not particularly limited as long as it is an organic compound that can stably maintain a gaseous state at the pressure and temperature in each step of forming the organic-inorganic hybrid film.
- the organic compound is not limited to an organic compound that is gaseous under standard conditions (temperature of 25° C., pressure of 100 KPa).
- the organic compound may be an organic compound that becomes a gas when heated (generally below the upper limit temperature at which the film substrate is practically usable) and/or when decompressed. From the viewpoint of workability when mixing the sputtering gas and the organic compound gas to prepare a mixed gas of both, the organic compound is preferably a gaseous organic compound under standard conditions (temperature of 25° C., pressure of 100 KPa). It may be a compound.
- the organic compound is to be applied to the organic-inorganic hybrid film from among organic compounds that can stably maintain a gaseous state at the pressure and temperature in each step of forming the organic-inorganic hybrid film. It can be appropriately selected in consideration of characteristics and functions.
- organic fluorine compounds examples include organic fluorine compounds.
- the organic fluorine compound is a compound having a fluorine-carbon bond. Typically, it is a compound having a structure in which one or more hydrogen atoms of an organic compound such as hydrocarbon are substituted with fluorine atoms.
- the organic fluorine compound may preferably be an organic compound that is gaseous under standard conditions (temperature of 25° C., pressure of 100 KPa).
- organic fluorine compound examples include saturated hydrocarbons such as tetrafluoromethane, trifluoromethane, difluoromethane, fluoromethane, and 1,1,1,2-tetrafluoroethane, which have one or more hydrogen atoms.
- organic compound one or a mixture of two or more thereof can be used.
- Substrate The method for producing the composite membrane of the present invention comprises: on at least one side of a substrate (i.e., on only one side of the substrate, or on both sides of the substrate) the composite membrane including forming
- the base material can be appropriately selected according to the use of the laminate or molded article having the composite film on at least one surface of the base material.
- the laminate having the composite film on at least one surface of the substrate or the molded article may be simply referred to as the "laminate.”
- laminate simply means the laminate or molded article having the organic-inorganic hybrid film on at least one surface of the substrate.
- the method for producing an organic-inorganic hybrid film of the present invention includes forming the organic-inorganic hybrid film on at least one surface of a substrate.
- the base material can be appropriately selected according to the application of the laminate or molded article having the organic-inorganic hybrid film on at least one surface of the base material.
- the laminate having the organic-inorganic hybrid film on at least one surface of the substrate or the molded article may be simply referred to as the "laminate.”
- the composite film forming surface of the base material may be smooth (entirely or partially) or may have a three-dimensional shape such as unevenness (entirely or partially).
- three-dimensional shape is meant a shape that generally includes a non-planar surface.
- the organic-inorganic hybrid film forming surface of the base material may be smooth (wholly or partially) or may have a three-dimensional shape such as unevenness (whole or partially).
- the substrate is, in one exemplary embodiment, a film, sheet, or plate.
- the base material examples include inorganic glass films, inorganic glass sheets, and inorganic glass plates such as soda lime glass, borosilicate glass, and quartz glass.
- the base material examples include cellulose ester resins such as triacetyl cellulose; polyester resins such as polyethylene terephthalate; cyclic hydrocarbon resins such as ethylene norbornene copolymer; polymethyl methacrylate, polyethyl methacrylate, and Acrylic resins such as vinylcyclohexane/(meth)methyl acrylate copolymer; aromatic polycarbonate resins; polyolefin resins such as polypropylene and 4-methyl-pentene-1; polyamide resins; polyarylate resins; type urethane acrylate resin; and polyimide resin film, resin sheet, or resin plate.
- These resin films include unstretched films, uniaxially stretched films, and biaxially stretched films.
- These resin films also include laminated resin films obtained by laminating two or more layers of one or more of these.
- These resin sheets include unoriented sheets, uniaxially oriented sheets, and biaxially oriented sheets.
- These resin sheets also include laminated resin sheets obtained by laminating two or more layers of one or more of these.
- These resin boards include laminated resin boards obtained by laminating two or more layers of one or more of these.
- the substrate one having a functional layer on at least one surface thereof may be used.
- the base material includes those having no functional layer on either side, those having a functional layer only on one side, and those having a functional layer on both sides.
- the surface on which the composite film is formed may be the surface on the side of the functional layer, or the surface on the side opposite to the functional layer.
- the substrate one having a functional layer on at least one surface of the resin film, the resin sheet, or the resin plate is used, and the surface on the functional layer side or the opposite side to the functional layer is used. may be used as the formation surface of the organic-inorganic hybrid film. That is, the composite film or the organic-inorganic hybrid film may be formed directly on the substrate without interposing the functional layer, or may be formed on the substrate through the functional layer.
- the functional layer may be a coating film (including a hard coat) formed using paint.
- the functional layer may be a film formed by a dry coating method such as a sputtering method, a vacuum deposition method, and a chemical vapor deposition method.
- the thickness of the inorganic glass film, inorganic glass sheet, or inorganic glass plate is not particularly limited, and can be set to any desired thickness.
- the thickness is usually 20 ⁇ m or more, preferably 50 ⁇ m or more.
- the thickness may be usually 0.8 mm or more, preferably 1 mm or more, and more preferably 1.5 mm or more.
- the thickness is usually 6 mm or less, preferably 4.5 mm or less, and more preferably 3 mm or less.
- the thickness of the resin film, resin sheet, or resin plate is not particularly limited, and can be set to any desired thickness. From the viewpoint of handleability of the laminate, the thickness is usually 20 ⁇ m or more, preferably 50 ⁇ m or more. When the laminate is used for applications that do not require high rigidity, the thickness may be usually 250 ⁇ m or less, preferably 150 ⁇ m or less, from the viewpoint of economy. When the laminate is used for applications requiring high rigidity, the thickness may be usually 300 ⁇ m or more, preferably 500 ⁇ m or more, more preferably 600 ⁇ m or more, from the viewpoint of maintaining rigidity. In addition, from the viewpoint of meeting the demand for thinner articles using the laminate, the thickness may be usually 1500 ⁇ m or less, preferably 1200 ⁇ m or less, more preferably 1000 ⁇ m or less.
- the base material may be colorless and transparent, or colorless and opaque.
- the base material may be colored and transparent, or colored and opaque (having hiding properties).
- the presence or absence of coloring of the base material and the transparency/non-transparency of the base material can be appropriately selected in consideration of the use of the laminate.
- the visible light transmittance of the base material is usually It may be 80% or more, preferably 85% or more, more preferably 88% or more, even more preferably 90% or more, most preferably 92% or more.
- the visible light transmittance is the area obtained by integrating the transmission spectrum over the wavelength range of 400 to 780 nm, and the transmission spectrum when it is assumed that the transmittance is 100% in the entire wavelength range of 400 to 780 nm. is the ratio to the area integrated over the interval of .
- Visible light transmittance for example, in accordance with JIS A5759: 2008 6.4 visible light transmittance test, can be measured using a spectrophotometer "SolidSpec-3700" (trade name) manufactured by Shimadzu Corporation. can.
- the thickness of the composite film can be appropriately selected in consideration of the properties and functions to be imparted to the composite film and the use of the laminate. From the viewpoint of crack resistance, the thickness of the composite film may be usually 1 ⁇ m or less, preferably 500 nm or less, more preferably 200 nm or less, even more preferably 150 nm or less, and most preferably 120 nm or less. On the other hand, the thickness of the composite film is usually 1 nm or more, preferably 10 nm or more, more preferably 20 nm or more, still more preferably 30 nm or more, and most preferably, from the viewpoint of reliably obtaining the properties and functions to be imparted by the composite film. may be 40 nm or greater.
- the thickness of the organic-inorganic hybrid film can be appropriately selected in consideration of the properties and functions to be imparted to the organic-inorganic hybrid film and the use of the laminate. From the viewpoint of crack resistance, the thickness of the organic-inorganic hybrid film may be usually 1 ⁇ m or less, preferably 500 nm or less, more preferably 200 nm or less, still more preferably 150 nm or less, and most preferably 120 nm or less.
- the thickness of the organic-inorganic hybrid film is usually 1 nm or more, preferably 10 nm or more, more preferably 20 nm or more, and still more preferably 30 nm, from the viewpoint of reliably obtaining the properties and functions to be imparted by the organic-inorganic hybrid film. More preferably, it may be 40 nm or more.
- targets 9 and 9' made of inorganic substances are mounted on target installation jigs 8 and 8', respectively.
- the inorganic substance target 9 and the inorganic substance target 9' may be the same inorganic substance target, or may be different inorganic substance targets.
- the inorganic substance target 9 and the inorganic substance target 9′ may preferably be the same inorganic substance target from the viewpoint of the uniformity of the composition of the organic-inorganic hybrid film.
- the film substrate 10 is passed through. That is, the film roll 12 of the film substrate 10 is set on the delivery roll 2, and a winding tube (not shown) is set on the take-up roll 5, the film substrate 10 is delivered from the film roll 12, and the transport roll 3 It is held by the sputtering roll 4 via the transfer roll 3 ′ and can be wound up by the winding tube set on the winding roll 5 via the transfer roll 3 ′.
- the film substrate 10 may be passed before the inorganic substance targets 9 and 9' are attached to the target installation jigs 8 and 8', respectively.
- the inside of the sputtering chamber 1 is evacuated from the exhaust port 7 by an exhaust device to reduce the pressure in the sputtering chamber 1 to a predetermined pressure or less during film formation.
- the reduced pressure may be usually about 10 -5 to 10 -2 Pa, preferably about 10 -4 to 6 ⁇ 10 -3 Pa.
- a mixed gas of the above sputtering gas and the above organic compound gas is introduced into the sputtering chamber 1 from the sputtering gas inlet 6 so that the inside of the sputtering chamber 1 is at a predetermined pressure (above the reduced pressure: above reduced pressure or above).
- the sputtering gas and the organic compound gas may be separately prepared, and the two gas flows may be merged and introduced while being mixed, or the mixed gas of the sputtering gas and the organic compound may be prepared in advance, You can introduce this.
- the opening degree of the exhaust port 7 may be feedback-controlled to keep the sputtering pressure constant.
- the mixing ratio of the sputtering gas and the organic compound gas is such that the composition of the organic-inorganic hybrid film (the ratio of the number of atoms derived from the inorganic substance to the number of atoms derived from the organic compound) is a desired composition. It can be determined as appropriate from the viewpoint of making it possible and the viewpoint of sputtering efficiency.
- the mixing ratio of the sputtering gas and the organic compound gas (volume of the sputtering gas/volume of the organic compound gas: converted to standard conditions (0° C. and 1 atm)) depends on the type of the organic compound.
- the sputtering gas is not particularly limited as long as it is a gas that can be used for sputtering, and may be any known sputtering gas.
- the sputtering gas include an inert gas such as at least one selected from argon and krypton; and a mixed gas of this and at least one other gas such as oxygen and nitrogen. be able to.
- a mixed gas of the inert gas and other gas is used as the sputtering gas, there is no particular limitation, but the mixed volume ratio may be 1/99 to 99/1 or 5/95 to 95/5. .
- the organic compound in the case of using an organic compound that becomes gaseous by heating (generally below the upper limit temperature at which the film substrate can be actually used) or/and depressurization, the organic compound is heated to a predetermined temperature and pressure in advance to be gaseous. Needless to say, it is used in the state of In this case, it is preferable that the temperature in the sputtering chamber 1 is also set to a predetermined temperature.
- the predetermined pressure (sputtering pressure) in the sputtering chamber 1 during the film formation is usually 0.05 to 5 Pa, preferably 0.1 to 5 Pa, from the viewpoint of stabilizing discharge and enabling continuous film formation. It may be 1 Pa.
- predetermined power usually, high-frequency power
- predetermined power is applied to each of the targets 9 and 9' made of an inorganic substance to cause discharge, and when the discharge state is stabilized, the film substrate 10 is moved at a predetermined line speed.
- An organic-inorganic hybrid film is formed on the surface of the film substrate 10 while the film substrate 10 is being heated.
- cooling water having a predetermined flow rate and a predetermined temperature is supplied to the target installation jigs 8 and 8' to control the temperature of the inorganic material targets 9 and 9' to a predetermined temperature.
- the reason why the formed sputtered film is an organic-inorganic hybrid film in spite of the fact that power is directly applied only to the target of an inorganic substance is as follows.
- the organic compound gas present in the vicinity of the inorganic target is captured by the magnetic field generated by the application of power to the inorganic target, and the sputtering gas and plasma present at high density within the magnetic field.
- the target of the inorganic substance is energized and sputtered, and the vapor of the organic compound is concomitantly sputtered.
- the composition of the organic-inorganic hybrid film depends on the power supplied to the inorganic substance targets 9 and 9 ′, the sputtering gas and the A desired composition can be obtained by adjusting the mixing ratio of the organic compound and the gas. Note that the relationship between the amount of input power, the mixing ratio, and the composition of the film can be obtained by performing a preliminary experiment.
- the film thickness of the organic-inorganic hybrid film depends on the electric power supplied to the inorganic substance targets 9 and 9′, the mixing ratio of the sputtering gas and the organic compound gas, and the mixed gas of the sputtering gas and the organic compound gas.
- a desired film thickness can be obtained by adjusting the flow rate of (the pressure in the sputtering chamber 1 during film formation) and the line speed (running speed of the film substrate 10).
- the relationship between the input power amount, the mixing ratio, the flow rate of the mixed gas, and the line speed and the film thickness can be obtained by performing a preliminary experiment.
- the film substrate 10 is reciprocated at a predetermined distance and passed through the position facing the inorganic substance targets 9, 9' of the sputtering roll 4 (that is, the position where the organic-inorganic hybrid film is formed) two or more times. good too.
- the line speed running speed of the film substrate 10
- the film thickness of the organic-inorganic hybrid film is to be increased, it becomes easy to ensure a stable line speed.
- the thickness of the organic-inorganic hybrid film is the function to be imparted to the organic-inorganic hybrid film, and the laminate or the molded body having the organic-inorganic hybrid film on at least one surface of the film substrate. It can be determined as appropriate in consideration of the intended use.
- the film thickness of the organic-inorganic hybrid film is usually 1 nm or more, preferably 10 nm or more, more preferably 20 nm or more, from the viewpoint of lowering the ultraviolet transmittance. , more preferably 30 nm or more, and most preferably 40 nm or more.
- this film thickness may be usually 1 ⁇ m or less, preferably 500 nm or less, more preferably 200 nm or less, still more preferably 150 nm or less, and most preferably 120 nm or less.
- the organic-inorganic hybrid film After forming the organic-inorganic hybrid film, at a temperature of 50° C. or higher, preferably 80° C. or higher, more preferably 100° C. or higher, and a temperature lower than the temperature considering the heat resistance of the film substrate 10, from the viewpoint of workability and productivity. , preferably at a temperature of 150° C. or less. Thereby, the characteristics of the organic-inorganic hybrid film can be stabilized.
- Second Embodiment An example of an embodiment of the method for producing an organic-inorganic hybrid film of the present invention using a batch-type sputtering apparatus, the conceptual diagram of which is shown in FIG. 3, will be described.
- inorganic material targets 16 and 16' are mounted on target installation jigs 15 and 15', respectively.
- the inorganic substance target 16 and the inorganic substance target 16' may be the same inorganic substance target, or may be different inorganic substance targets.
- the inorganic substance target 16 and the inorganic substance target 16' may preferably be the same inorganic substance target from the viewpoint of the uniformity of the composition of the organic-inorganic hybrid film.
- the predetermined rotational speed of the sputtering table 18 may be generally 1 to 1000 rpm, preferably 2 to 50 rpm.
- the rotation speed may be constant, or the rotation speed may be changed as desired.
- the inside of the sputtering chamber 20 is evacuated from the exhaust port 21 by an exhaust device to reduce the pressure in the sputtering chamber 20 to a predetermined pressure or less during film formation.
- the reduced pressure may be usually about 10 -5 to 10 -2 Pa, preferably about 10 -4 to 5 ⁇ 10 -3 Pa.
- a mixed gas of the sputtering gas and the organic compound gas is introduced from the sputtering gas inlet 22 into the sputtering chamber 20 so that the inside of the sputtering chamber 20 is at a predetermined pressure (the reduced pressure or higher: above reduced pressure or above).
- the sputtering gas and the organic compound gas may be separately prepared, and the two gas flows may be merged and introduced while being mixed, or the mixed gas of the sputtering gas and the organic compound may be prepared in advance, You can introduce this.
- the sputtering pressure may be kept constant by feedback-controlling the opening degree of the exhaust port 21 while fixing the introduction amount of the mixed gas.
- the mixing ratio of the sputtering gas and the organic compound gas is such that the composition of the organic-inorganic hybrid film (the ratio of the number of atoms derived from the inorganic substance to the number of atoms derived from the organic compound) is a desired composition. It can be determined as appropriate from the viewpoint of making it possible and the viewpoint of sputtering efficiency.
- the mixing ratio of the sputtering gas and the organic compound gas (volume of the sputtering gas/volume of the organic compound gas: converted to standard conditions (0° C. and 1 atm)) depends on the type of the organic compound.
- the sputtering gas is not particularly limited as long as it is a gas that can be used for sputtering, and may be any known sputtering gas.
- the sputtering gas include an inert gas such as at least one selected from argon and krypton; and a mixed gas of this and at least one other gas such as oxygen and nitrogen. be able to.
- a mixed gas of the inert gas and other gas is used as the sputtering gas, there is no particular limitation, but the mixed volume ratio may be 1/99 to 99/1 or 5/95 to 95/5. .
- the gaseous compound in the case of using an organic compound that becomes gaseous by heating (usually below the upper limit temperature at which the substrate can actually be used) and/or under reduced pressure, the gaseous compound is heated to a predetermined temperature and pressure in advance. Needless to say, it is used as a state. In this case, it is preferable that the temperature in the sputtering chamber 20 is also set to a predetermined temperature.
- the predetermined pressure (sputtering pressure) in the sputtering chamber 20 during film formation is usually 0.05 to 5 Pa, preferably 0.1 to 5 Pa, from the viewpoint of stabilizing discharge and enabling continuous film formation. It may be 1 Pa.
- a predetermined power (usually, high-frequency power) is applied to the targets 16 and 16' made of inorganic substances to cause discharge, and when the discharge state is stabilized, the shutters 17 and 17' are opened to sputter each target. Then, an organic-inorganic hybrid film is formed on the surface of the substrate 19 . At this time, cooling water having a predetermined flow rate and a predetermined temperature is supplied to the target installation jigs 15 and 15' to control the temperature of the inorganic material targets 16 and 16' to a predetermined temperature.
- the surface of the substrate 19 can be kept free of such contaminants.
- the composition of the organic-inorganic hybrid film depends on the power input to the inorganic substance targets 16 and 16 ′, the sputtering gas and the organic
- a desired composition can be obtained by adjusting the mixing ratio of the compound gas and the flow rate of the mixed gas of the sputtering gas and the organic compound gas (the pressure in the sputtering chamber 20 during film formation).
- the relationship between the amount of power input, the mixing ratio, the flow rate of the mixed gas, and the film composition can be obtained by performing a preliminary experiment.
- the film thickness of the organic-inorganic hybrid film depends on the electric power supplied to the inorganic substance targets 16 and 16′, the mixing ratio of the sputtering gas and the organic compound gas, and the mixed gas of the sputtering gas and the organic compound gas.
- a desired film thickness can be obtained by adjusting the flow rate of (the pressure in the sputtering chamber 20 during film formation) and the film formation time. Note that the relationship between the amount of power input, the mixing ratio, the flow rate of the mixed gas, and the film formation time and the film thickness can be obtained by performing a preliminary experiment.
- the thickness of the organic-inorganic hybrid film depends on the function to be imparted to the organic-inorganic hybrid film, and the use of the laminate or the molded product having the organic-inorganic hybrid film on at least one surface of the base material. can be determined as appropriate in consideration of
- the film thickness of the organic-inorganic hybrid film is usually 1 nm or more, preferably 10 nm or more, more preferably 20 nm or more, from the viewpoint of lowering the ultraviolet transmittance. , more preferably 30 nm or more, and most preferably 40 nm or more.
- this film thickness may be usually 1 ⁇ m or less, preferably 500 nm or less, more preferably 200 nm or less, still more preferably 150 nm or less, and most preferably 120 nm or less.
- the organic-inorganic hybrid film After forming the organic-inorganic hybrid film, at a temperature of 50° C. or higher, preferably 80° C. or higher, more preferably 100° C. or higher, and a temperature lower than the temperature considering the heat resistance of the substrate 19, from the viewpoint of workability and productivity, It is preferable to anneal, preferably at a temperature of 150° C. or less. Thereby, the characteristics of the organic-inorganic hybrid film can be stabilized.
- XPS analysis can be performed, for example, by using an XPS analyzer and using K ⁇ rays of aluminum or K ⁇ rays of magnesium as X-rays.
- XPS analysis reference can be made to the following references and the like. References: M. P. Seah and W. A. Derch, Surface and Interface Analysis 1, 2 (1979)
- the sputtered film thickness was determined by a preliminary experiment. First, a heat-resistant, low-outgassing adhesive tape (“Kapton Tape P-221” (trade name) manufactured by Nitto Denko Co., Ltd.) is partially attached to the substrate in advance, and after sputtering, it is peeled off to form a film. A thick step was formed. Using a small surface roughness measuring machine "SJ-411" (trade name) manufactured by Mitutoyo Corporation, the shape profile of the stepped portion is measured at a measurement speed of 0.5 mm / s and a measurement distance of 1.5 mm. The read step was taken as the sputtered film thickness.
- Kapton Tape P-221 (trade name) manufactured by Nitto Denko Co., Ltd.)
- the conditions were an electron extraction angle of 90 degrees, a pass energy of 50 eV, a measurement range of 678 to 698 eV, an energy step of 0.100 eV, a step time of 50 ms, and 10 measurements.
- F1s narrow scan spectra were measured at .
- Raw materials used A target of a solid substance under standard conditions (temperature 25° C., pressure 100 KPa)
- A-1 A disk shape with a diameter of 76.2 mm and a thickness of 3 mm obtained by sintering cerium dioxide manufactured by USTRON Co., Ltd. target.
- Purity 4N. A-2) A rectangular parallelepiped target having a length of 127 mm, a width of 380 mm, and a thickness of 3 mm obtained by sintering cerium dioxide manufactured by USTRON.
- Purity 4N. A-shaped target of polydimethylsiloxane (silicone resin containing no fluorine atoms) having a diameter of 76.2 mm and a thickness of 3 mm.
- C-1 A smooth soda-lime glass plate manufactured by Matsunami Glass Industry Co., Ltd. (product name: microslide glass, polished water edge, thickness: 1.0 mm, dimensions: 40 ⁇ 40 mm).
- C-2) A 125 ⁇ m-thick double-sided easy-adhesive biaxially stretched polyethylene terephthalate-based resin film “Lumirror” (trade name) manufactured by Toray Industries, Inc.;
- Example 1 An organic-inorganic hybrid film was formed on one surface of (C-1) using the above (A-1) and the above (B-1) using a batch system sputtering apparatus. First, the above (A-1) was mounted on the target installation jig of the above sputtering apparatus. Next, the pressure inside the sputtering chamber of the sputtering apparatus was reduced to 3.0 ⁇ 10 ⁇ 3 Pa.
- the gas flow (volumetric flow rate: 23.4 sccm) of argon gas (purity grade of 99.999% or higher) as a sputtering gas and the above (B-1) gas flow (volumetric flow rate: 2.6 sccm) are combined,
- the mixture was introduced into the sputtering chamber while being mixed, and the shutter opening of the exhaust pipe was adjusted so that the pressure in the sputtering chamber was 0.8 Pa.
- power is applied to the above (A-1) under the condition of an input power of 200 W (input power amount per unit area is 4.4 W/cm 2 ), sputtering is performed, and one surface of the above (C-1) is performed. A sputtered film was formed thereon.
- the film formation time was 30 minutes, and the film formation conditions were such that the thickness of the sputtered film was 165 nm.
- An XPS analysis was performed on the sputtered film. Analytical results are shown in FIGS. In the F1s narrow scan spectrum of FIG. 4, a peak derived from the F—Ce bond appears at 685.7 eV, so the fluorine atom derived from tetrafluoromethane modifies cerium dioxide to form cerium trifluoride. I know it happened. Further, the atomic number ratio (F/Ce) between fluorine and cerium calculated from the wide scan spectrum of FIG. 5 was 3.7.
- the sputtered film was an organic-inorganic hybrid film, that is, an organic-inorganic hybrid film could be formed by the method of the present invention.
- the unit of volumetric flow rate, "sccm” is the volume of gas flowing in one minute normalized under standard conditions (temperature of 0° C., 1 atm).
- Example 2 Except that the gas flow of argon gas (volume flow rate: 20.8 sccm) as the sputtering gas and the gas flow (B-1) (volume flow rate: 5.2 sccm) were merged and introduced into the sputtering chamber while being mixed.
- a sputtered film was formed in the same manner as in Example 1. At this time, the film formation time was 30 minutes, and the film formation conditions were such that the thickness of the sputtered film was 200 nm.
- An XPS analysis was performed on the sputtered film. Analytical results are shown in FIGS. In the F1s narrow scan spectrum of FIG.
- Example 3 Using a roll-to-roll sputtering apparatus whose conceptual diagram is shown in FIG. 1, using the above (A-2) and the above (B-1), on one surface of the above (C-2) An organic-inorganic hybrid film was formed. First, the above (C-2) was passed through the sputtering apparatus, and then the above (A-2) (target 9) was mounted on the target installation jig 8. Note that the target installation jig 8' was not used. That is, the number of (A-2) used was one. Next, the pressure in the sputtering chamber 1 of the sputtering apparatus was reduced to 5.0 ⁇ 10 ⁇ 3 Pa.
- the gas flow (volumetric flow rate: 190 sccm) of argon gas (purity grade of 99.999% or higher) as a sputtering gas and the gas flow (volumetric flow rate: 10 sccm) of (B-1) are combined and mixed.
- the gas was introduced into the sputtering chamber 1, and the opening degree of the shutter of the exhaust port 7 was adjusted so that the pressure in the sputtering chamber 1 was 0.4 Pa.
- the above (C-2) while winding the above (C-2) at a line speed of 1.0 m / min, the above (A-2) (target 9) was supplied with power of 1500 W (input power amount per unit area of 3.0 m).
- Example 4 A sputtered film was formed in the same manner as in Example 3, except that the volume flow rate of the argon gas flow was changed to 199 sccm and the flow rate of the gas flow (B-1) was changed to 1 sccm. The film formation conditions were such that the thickness of the sputtered film was 50 nm.
- An XPS analysis was performed on the sputtered film. Analytical results are shown in FIGS. In the F1s narrow scan spectrum of FIG. 10, a peak derived from the F—Ce bond appears at 681.5 eV, so fluorine atoms derived from tetrafluoromethane modify cerium dioxide to produce cerium trifluoride. I found out. Further, the atomic number ratio (F/Ce) between fluorine and cerium calculated from the wide scan spectrum of FIG. 11 was 1.7. From these results, it was confirmed that an organic-inorganic hybrid film was formed.
- a method of manufacturing a composite membrane comprising: using a sputtering device, Using a gas of a first organic compound target and a second organic compound (which may be the same or different organic compound as the first organic compound, but is usually an organic compound different from the first organic compound), (1) a step of mounting the first organic compound target on a target installation jig of the sputtering apparatus; (2) reducing the pressure in the sputtering chamber of the sputtering apparatus to a first predetermined pressure; (3) A mixed gas of the sputtering gas and the second organic compound gas is introduced into the sputtering chamber of the sputtering apparatus so that the pressure in the sputtering chamber reaches a second predetermined pressure equal to or higher than the first predetermined pressure.
- the gas of the second organic compound is a compound having a structure in which one or more hydrogen atoms of a saturated hydrocarbon are substituted with fluorine atoms, and is gaseous under standard conditions (temperature 25 ° C., pressure 100 KPa).
- Example 5 A sputtered film was formed in the same manner as in Example 1 except that (A-3) was used instead of (A-1). At this time, the film formation time was 30 minutes, and the film formation conditions were such that the thickness of the sputtered film was 200 nm. When the sputtered film was analyzed by an FT-IR specular reflection method, a peak derived from a C—F bond appeared. From this, it was confirmed that the fluorine atoms derived from tetrafluoromethane modified the silicone resin, that is, the formation of a composite film.
- Sputtering chamber 2 Feeding roll 3, 3': Transfer roll 4: Sputtering roll 5: Winding roll 6: Sputtering gas introduction port 7: Exhaust port 8, 8': Target installation jig 9, 9': Target 10: Film substrate 11: Laminate 12, 12': Film roll 13: Anti-adhesion plate 14: Anti-adhesion plate mounting jig 15, 15': Target installation jig 16, 16': Target 17, 17': Shutter 18: Sputter table 19: Base Material 20: Sputtering Chamber 21: Exhaust Port 22: Sputtering Gas Inlet
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Abstract
Description
本発明の更なる課題は、新規な有機無機ハイブリッド膜の製造方法を提供することにある。
[1].
複合膜の製造方法であって、
スパッタリング装置を使用し、
(A)標準状態(温度25℃、圧力100KPa)で固体の物質のターゲット、及び
(B)スパッタガスとの混合気体を調製可能な物質の気体を用い、
(1)上記スパッタリング装置のターゲット設置冶具に上記(A)ターゲットを装着する工程;
(2)上記スパッタリング装置のスパッタ室内を第1の所定の圧力に減圧する工程;
(3)スパッタガスと上記(B)気体との混合気体を、上記スパッタリング装置のスパッタ室内に、該スパッタ室内が第1の所定の圧力以上である第2の所定の圧力となるように導入する工程;及び、
(4)上記(A)ターゲットに電力を投入し、スパッタリングすることにより、基材の面の上に上記複合膜を形成する工程
を含む、上記製造方法。
[2].
上記スパッタリング装置が、ロール・トゥ・ロール方式のスパッタリング装置である、[1]項に記載の製造方法。
[3].
上記混合気体の混合比(上記スパッタガスの体積/上記(B)気体の体積:標準状態(0℃及び1気圧)換算)が、60/40~99.999/0.001である、[1]項又は[2]項に記載の製造方法。
[4].
上記(B)気体が有機化合物の気体を含む、[1]~[3]項の何れか1項に記載の製造方法。
[5].
上記有機化合物の気体が、飽和炭化水素の1個又は2個以上の水素原子が弗素原子に置換された構造を有する化合物であって標準状態(温度25℃、圧力100KPa)で気体の化合物、及び不飽和炭化水素の1個又は2個以上の水素原子が弗素原子に置換された構造を有する化合物であって標準状態(温度25℃、圧力100KPa)で気体の化合物からなる群から選択される1種以上の化合物の気体を含む、[4]項に記載の製造方法。
[6].
上記(A)ターゲットが無機物質のターゲットである、[1]~[5]項の何れか1項に記載の製造方法。
[7].
上記無機物質のターゲットが2.6~3.7eVのバンドギャップを有する無機物質を含む、[6]項に記載の製造方法。
[8].
上記無機物質のターゲットが酸化セリウムを含む、[6]項又は[7]項に記載の製造方法。
[9].
上記スパッタリング装置が、ロール・トゥ・ロール方式のスパッタリング装置であり;
上記混合気体の混合比(上記スパッタガスの体積/上記(B)気体の体積:標準状態(0℃及び1気圧)換算)が、60/40~99.999/0.001であり;
上記(B)気体が有機化合物の気体を含み;
上記有機化合物の気体が、飽和炭化水素の1個又は2個以上の水素原子が弗素原子に置換された構造を有する化合物であって標準状態(温度25℃、圧力100KPa)で気体の化合物、及び不飽和炭化水素の1個又は2個以上の水素原子が弗素原子に置換された構造を有する化合物であって標準状態(温度25℃、圧力100KPa)で気体の化合物からなる群から選択される1種以上の化合物の気体を含み;
上記(A)ターゲットが無機物質のターゲットであり;
上記無機物質のターゲットが2.6~3.7eVのバンドギャップを有する無機物質を含み;
上記無機物質のターゲットが酸化セリウムを含む、[1]項に記載の製造方法。
[10].
上記(A)ターゲットが有機化合物のターゲットである、[1]~[5]項の何れか1項に記載の製造方法。
[11].
上記有機化合物のターゲットが、シリコーン樹脂を含む、[10]項に記載の製造方法。
[12].
上記スパッタリング装置が、ロール・トゥ・ロール方式のスパッタリング装置であり;
上記混合気体の混合比(上記スパッタガスの体積/上記(B)気体の体積:標準状態(0℃及び1気圧)換算)が、60/40~99.999/0.001であり;
上記(B)気体が有機化合物の気体を含み;
上記有機化合物の気体が、飽和炭化水素の1個又は2個以上の水素原子が弗素原子に置換された構造を有する化合物であって標準状態(温度25℃、圧力100KPa)で気体の化合物、及び不飽和炭化水素の1個又は2個以上の水素原子が弗素原子に置換された構造を有する化合物であって標準状態(温度25℃、圧力100KPa)で気体の化合物からなる群から選択される1種以上の化合物の気体を含み;
上記(A)ターゲットが有機化合物のターゲットであり;
上記有機化合物のターゲットがシリコーン樹脂を含む、[1]項に記載の製造方法。
[1a].
有機無機ハイブリッド膜の製造方法であって、
スパッタリング装置を使用し、
無機物質のターゲットと有機化合物の気体を用い、
(1)上記スパッタリング装置のターゲット設置冶具に上記無機物質のターゲットを装着する工程;
(2)上記スパッタリング装置のスパッタ室内を第1の所定の圧力に減圧する工程;
(3)スパッタガスと上記有機化合物の気体との混合気体を、上記スパッタリング装置のスパッタ室内に、該スパッタ室内が第1の所定の圧力以上である第2の所定の圧力となるように導入する工程;及び、
(4)上記無機物質のターゲットに電力を投入し、スパッタリングすることにより、基材の面の上に上記有機無機ハイブリッド膜を形成する工程
を含む、上記製造方法。
[2a].
上記スパッタリング装置が、ロール・トゥ・ロール方式のスパッタリング装置である、[1a]項に記載の製造方法。
[3a].
上記混合気体の混合比(上記スパッタガスの体積/上記有機化合物の気体の体積:標準状態(0℃及び1気圧)換算)が、60/40~99.999/0.001である、[1a]項又は[2a]項に記載の製造方法。
[4a].
上記有機化合物の気体が、飽和炭化水素の1個又は2個以上の水素原子が弗素原子に置換された構造を有する化合物であって標準状態(温度25℃、圧力100KPa)で気体の化合物、及び不飽和炭化水素の1個又は2個以上の水素原子が弗素原子に置換された構造を有する化合物であって標準状態(温度25℃、圧力100KPa)で気体の化合物からなる群から選択される1種以上の化合物の気体を含む、[1a]~[3a]項の何れか1項に記載の製造方法。
[5a].
上記無機物質のターゲットが、2.6~3.7eVのバンドギャップを有する無機物質を含む、[1a]~[4a]項の何れか1項に記載の製造方法。
[6a].
上記無機物質のターゲットが酸化セリウムを含む、[1a]~[5a]項の何れか1項に記載の製造方法。
本明細書において、「有機無機ハイブリッド膜」とは、無機物質に由来する原子(分子を構成していてよい)、及び有機化合物に由来する原子(分子を構成していてよい)を含む膜を意味する。
スパッタリング装置を使用し、
(A)標準状態(温度25℃、圧力100KPa)で固体の物質のターゲットと
(B)スパッタガスとの混合気体を調製可能な物質の気体を用い、
(1)上記スパッタリング装置のターゲット設置冶具に上記(A)ターゲットを装着する工程;
(2)上記スパッタリング装置のスパッタ室内を第1の所定の圧力に減圧する工程;
(3)スパッタガスと上記(B)気体との混合気体を、上記スパッタリング装置のスパッタ室内に、該スパッタ室内が第1の所定の圧力以上である第2の所定の圧力となるように導入する工程;及び、
(4)上記(A)ターゲットに電力を投入し、スパッタリングすることにより、基材の面の上に上記複合膜を形成する工程
を含む。
有機無機ハイブリッド膜以外の複合膜を製造する場合には、「有機無機ハイブリッド膜」を「複合膜」と、「無機化合物のターゲット」を「(A)標準状態(温度25℃、圧力100KPa)で固体の物質のターゲット」と、「有機化合物の気体」を「(B)スパッタガスとの混合気体を調製可能な物質の気体」と適宜読み替えて、本発明の複合膜の製造方法を実施すればよいことは言うまでもない。
本発明の複合膜の製造方法は、スパッタリング装置を使用する。
また、本発明の有機無機ハイブリッド膜の製造方法は、スパッタリング装置を使用する。該スパッタリング装置としては、特に制限されず、公知のスパッタリング装置を使用することができる。上記スパッタリング装置としては、有機無機ハイブリッド膜を生産性良く形成する観点から、フィルムロールからフィルム基材を繰り出し、該フィルム基材の面の上に有機無機ハイブリッド膜を形成した後、フィルムロールとして巻き取る機構を有するスパッタリング装置(以下、「ロール・トゥ・ロール方式のスパッタリング装置」と言うことがある)が好ましい。
本発明の複合膜の製造方法は、(A)標準状態(温度25℃、圧力100KPa)で固体の物質のターゲットを用いる。
即ち、本発明の複合膜の製造方法により生産される複合膜は、上記(A)標準状態(温度25℃、圧力100KPa)で固体の物質に由来する原子を含む。
有機化合物の例には、シリコーン樹脂が包含される。該シリコーン樹脂は、シロキサン結合(Si-O-Si)を主骨格とする高分子化合物である。
上記シリコーン樹脂としては、上記構造を有する限りは特に限定されないが、例えば、ポリジメチルシロキサン、ポリジエチルシロキサン、ポリメチルフェニルシロキサン、及びポリジフェニルシロキサン、並びにこれらの変性体などをあげることができる。上記シリコーン樹脂としては、これらの1種又は2種以上の混合物を用いることができる。
本発明の有機無機ハイブリッド膜の製造方法は、無機物質のターゲットを用いる。
即ち、本発明の有機無機ハイブリッド膜の製造方法により生産される有機無機ハイブリッド膜は、上記無機物質に由来する原子を含む。
本発明の複合膜の製造方法は、(B)スパッタガスとの混合気体を調製可能な物質の気体を用いる。
即ち、本発明の複合膜の製造方法により生産される複合膜は、上記(B)スパッタガスとの混合気体を調製可能な物質に由来する原子を含む。
上記(B)スパッタガスとの混合気体を調製可能な物質は、標準状態(温度25℃、圧力100KPa)で気体の物質に限定されない。
上記(B)スパッタガスとの混合気体を調製可能な物質は、加温(通常、上記フィルム基材の実使用が可能な上限の温度以下)、又は/及び減圧により気体となる物質であってよい。
上記(B)スパッタガスとの混合気体を調製可能な物質は、上記スパッタガスと上記(B)スパッタガスとの混合気体を調製可能な物質の気体とを混合し、両者の混合気体を調製する際の作業性の観点から、好ましくは標準状態(温度25℃、圧力100KPa)で気体の物質であってよい。
本発明の有機無機ハイブリッド膜の製造方法は、有機化合物の気体を用いる。
即ち、本発明の有機無機ハイブリッド膜の製造方法により生産される有機無機ハイブリッド膜は、上記有機化合物の気体に由来する原子を含む。
本発明の複合膜の製造方法は、基材の少なくとも一方の面の上に(すなわち、基材の一方の面の上のみに、または基材の両方の面の上に)上記複合膜を形成することを含む。
上記基材は、該基材の少なくとも一方の面の上に上記複合膜を有する積層体又は成形体の用途に応じて適宜選択することができる。以下、上記基材の少なくとも一方の面の上に上記複合膜を有する上記積層体又は上記成形体の意味で単に「上記積層体」ということがある。ここで、単に「上記積層体」というとき、上記基材の少なくとも一方の面の上に上記有機無機ハイブリッド膜を有する上記積層体又は上記成形体の意味も含んでいることに留意されたい。
本発明の有機無機ハイブリッド膜の製造方法は、基材の少なくとも一方の面の上に上記有機無機ハイブリッド膜を形成することを含む。
上記基材は、該基材の少なくとも一方の面の上に上記有機無機ハイブリッド膜を有する積層体又は成形体の用途に応じて適宜選択することができる。以下、上記基材の少なくとも一方の面の上に上記有機無機ハイブリッド膜を有する上記積層体又は上記成形体の意味で単に「上記積層体」ということがある。
上記基材の上記有機無機ハイブリッド膜形成面は、(全体または一部が)平滑であってもよく、(全体または一部が)凹凸などの三次元形状を有するものであってもよい。
上記基材は、典型的な実施形態の1つにおいて、フィルム、シート、又は板である。
上記複合膜の形成面は該機能層側の面であってもよく、上記機能層とは反対側の面であってもよい。
上記基材としては、上記樹脂フィルム、上記樹脂シート、又は上記樹脂板の少なくとも一方の面の上に、機能層を有するものを用い、該機能層側の面、又は上記機能層とは反対側の面を上記有機無機ハイブリッド膜の形成面としてもよい。
すなわち、上記複合膜または上記有機無機ハイブリッド膜は、基材上に機能層を介することなく直接形成されるか、または機能層を介してその上に形成されるかのいずれかであってよい。
上記複合膜の厚みは、耐クラック性の観点から、通常1μm以下、好ましくは500nm以下、より好ましくは200nm以下、更に好ましくは150nm以下、最も好ましくは120nm以下であってよい。
一方、上記複合膜の厚みは、上記複合膜により付与しようとする特性、機能を確実に得る観点から、通常1nm以上、好ましくは10nm以上、より好ましくは20nm以上、更に好ましくは30nm以上、最も好ましくは40nm以上であってよい。
上記有機無機ハイブリッド膜の厚みは、耐クラック性の観点から、通常1μm以下、好ましくは500nm以下、より好ましくは200nm以下、更に好ましくは150nm以下、最も好ましくは120nm以下であってよい。
一方、上記有機無機ハイブリッド膜の厚みは、上記有機無機ハイブリッド膜により付与しようとする特性、機能を確実に得る観点から、通常1nm以上、好ましくは10nm以上、より好ましくは20nm以上、更に好ましくは30nm以上、最も好ましくは40nm以上であってよい。
本発明の有機無機ハイブリッド膜の製造方法であって、図1に概念図を示すロール・トゥ・ロール方式のスパッタリング装置を使用する実施形態の一例を説明する。
無機物質のターゲット9と無機物質のターゲット9’とは、有機無機ハイブリッド膜の組成の均一性の観点から、好ましくは同一の無機物質のターゲットであってよい。
本発明の有機無機ハイブリッド膜の製造方法であって、図3に概念図を示すバッチ方式のスパッタリング装置を使用する実施形態の一例を説明する。
無機物質のターゲット16と無機物質のターゲット16’とは、有機無機ハイブリッド膜の組成の均一性の観点から、好ましくは同一の無機物質のターゲットであってよい。
参考文献:M.P.Seah and W.A.Derch,Surface and Interface Analysis 1,2(1979)
(i)スパッタ膜厚
スパッタ膜厚は予備実験により求めた。先ず、予め基材に耐熱性・低アウトガス性の粘着テープ(日東電工株式会社製「カプトンテープ P-221」(商品名))を部分的に貼り付けておき、スパッタリング後にそれを剥離して膜厚分の段差を形成した。株式会社ミツトヨ製の小型表面粗さ測定機「SJ-411」(商品名)を用いて測定速度:0.5mm/s、測定距離:1.5mmで段差部の形状プロファイルを測定し、そこから読み取った段差をスパッタ膜厚とした。
XPS分析装置(サーモフィッシャーサイエンティフィック株式会社の「K-Alpha」(商品名))を使用し、エックス線として単色化したアルミニウムのKα線を使用し、照射径400μm、電子取り出し角度90度、パスエネルギー200eV、測定範囲-10~1350eV、エネルギーステップ1.000eV、1ステップの時間10ms、及び測定回数10回の条件でワイドスキャンスペクトルを測定した。
また弗素原子1s軌道(F1s)に帰属するエネルギー領域について、電子取り出し角度90度、パスエネルギー50eV、測定範囲678~698eV、エネルギーステップ0.100eV、1ステップの時間50ms、及び測定回数10回の条件でF1sナロースキャンスペクトルを測定した。
(A)標準状態(温度25℃、圧力100KPa)で固体の物質のターゲット
(A-1)USTRON株式会社の二酸化セリウムを焼結して得た直径76.2mm、厚み3mmの円盤形状のターゲット。純度4N。
(A-2)USTRON株式会社の二酸化セリウムを焼結して得た縦127mm、横380mm、厚み3mmの直方体形状のターゲット。純度4N。
(A-3)ポリジメチルシロキサン(弗素原子を含まないシリコーン樹脂)の直径76.2mm、厚み3mmの円盤形状のターゲット。
(B-1)テトラフルオロメタン(純度99.999%以上のグレード)。
(C-1)松浪硝子工業株式会社の平滑なソーダ石灰ガラス板(品名:マイクロスライドガラス、水縁磨品、厚み:1.0mm、寸法:40×40mm)。
(C-2)東レ株式会社の厚み125μmの両面易接着二軸延伸ポリエチレンテレフタレート系樹脂フィルム「ルミラー」(商品名)。
バッチ方式のスパッタリング装置を使用し、上記(A-1)と上記(B-1)を用いて、上記(C-1)の一方の面の上に有機無機ハイブリッド膜を形成した。先ず、上記スパッタリング装置のターゲット設置冶具に上記(A-1)を装着した。次に、上記スパッタリング装置のスパッタ室内を、圧力3.0×10-3Paに減圧した。次に、スパッタガスとしてのアルゴンガス(純度99.999%以上のグレード)の気体流(体積流量23.4sccm)と上記(B-1)の気体流(体積流量2.6sccm)とを合流、混合させながら上記スパッタ室内に導入し、該スパッタ室内の圧力が0.8Paとなるように排気配管部のシャッター開度を調整した。続いて、上記(A-1)に投入電力200W(単位面積当たりの投入電力量4.4W/cm2)の条件で電力を投入し、スパッタリングを行い、上記(C-1)の一方の面の上にスパッタ膜を形成した。このとき成膜時間は30分間であり、該スパッタ膜の厚みは165nmとなる成膜条件であった。
上記スパッタ膜についてXPS分析を行った。分析結果を図4、5に示す。図4のF1sナロースキャンスペクトルには、685.7eVにF-Ce結合に由来するピークが現れていることから、テトラフルオロメタンに由来する弗素原子が、二酸化セリウムを変性して三弗化セリウムを生じたことが分かった。また図5のワイドスキャンスペクトルから算出した弗素とセリウムとの原子数比(F/Ce)は3.7であった。これらの結果から、上記スパッタ膜は、有機無機ハイブリッド膜であること、即ち、本発明の方法により有機無機ハイブリッド膜を形成できることが分かった。
本明細書において、体積流量の単位「sccm」は、標準状態(温度0℃、1気圧)で規格化した1分間に流れる気体の体積である。
スパッタガスとしてのアルゴンガスの気体流(体積流量20.8sccm)と上記(B-1)の気体流(体積流量5.2sccm)とを合流、混合させながら上記スパッタ室内に導入したこと以外は、例1と同様にスパッタ膜を形成した。このとき成膜時間は30分間であり、該スパッタ膜の厚みは200nmとなる成膜条件であった。
上記スパッタ膜についてXPS分析を行った。分析結果を図6、7に示す。図6のF1sナロースキャンスペクトルには、例1と同様に、685.0eVにF-Ce結合に由来するピークが現れていることから、テトラフルオロメタンに由来する弗素原子が、二酸化セリウムを変性して三弗化セリウムを生じたことが分かった。また図7のワイドスキャンスペクトルから算出した弗素とセリウムとの原子数比(F/Ce)は7.4であった。これら結果から、上記スパッタ膜(有機無機ハイブリッド膜)の組成は、上記スパッタガスと上記有機化合物の気体との混合比により調節できることが確認された。
図1に概念図を示すロール・トゥ・ロール方式のスパッタリング装置を使用し、上記(A-2)と上記(B-1)を用いて、上記(C-2)の一方の面の上に有機無機ハイブリッド膜を形成した。
先ず、上記(C-2)を該スパッタリング装置に通紙した後、上記(A-2)(ターゲット9)をターゲット設置冶具8に装着した。
なお、ターゲット設置冶具8’は使用しなかった。即ち、使用した上記(A-2)は1個である。
次に、上記スパッタリング装置のスパッタ室内1を、圧力5.0×10-3Paに減圧した。
次に、スパッタガスとしてのアルゴンガス(純度99.999%以上のグレード)の気体流(体積流量190sccm)と上記(B-1)の気体流(体積流量10sccm)とを合流、混合させながら上記スパッタ室内1に導入し、該スパッタ室内1の圧力が0.4Paとなるように排気口7のシャッター開度を調整した。
続いて、上記(C-2)をライン速度1.0m/分の速度で引巻取りしながら、上記(A-2)(ターゲット9)に投入電力1500W(単位面積当たりの投入電力量3.1W/cm2)の条件で電力を投入し、スパッタリングを行い、上記(C-2)の一方の面の上にスパッタ膜を形成した。またこのとき上記(C-2)を所定距離で往復させて、スパッタロール4の上記(A-2)(ターゲット9)に対向する位置を9回通過するようにした。
上記スパッタ膜の厚みが50nmとなる成膜条件であった。
上記スパッタ膜についてXPS分析を行った。分析結果を図8、9に示す。図8のF1sナロースキャンスペクトルには、682.5eVにF-Ce結合に由来するピークが現れていることから、テトラフルオロメタンに由来する弗素原子が、二酸化セリウムを変性して三弗化セリウムを生じたことが分かった。また、図9のワイドスキャンスペクトルから算出した弗素とセリウムとの原子数比(F/Ce)は3.6であった。これら結果から、有機無機ハイブリッド膜が形成されたことを確認した。
上記アルゴンガスの気体流の流量を体積流量199sccmに、上記(B-1)の気体流の流量を1sccmに変更したこと以外は、例3と同様にしてスパッタ膜を形成した。
上記スパッタ膜の厚みが50nmとなる成膜条件であった。上記スパッタ膜についてXPS分析を行った。分析結果を図10、11に示す。
図10のF1sナロースキャンスペクトルには、681.5eVにF-Ce結合に由来するピークが現れていることから、テトラフルオロメタンに由来する弗素原子が二酸化セリウムを変性して三弗化セリウムを生じたことが分かった。また、図11のワイドスキャンスペクトルから算出した弗素とセリウムとの原子数比(F/Ce)は1.7であった。これら結果から、有機無機ハイブリッド膜が形成されたことを確認した。
[1].
複合膜の製造方法であって、
スパッタリング装置を使用し、
第1の有機化合物のターゲットと第2の有機化合物(第1の有機化合物と同じまたは異なる有機化合物であってよいが、通常、第1の有機化合物と異なる有機化合物である)の気体を用い、
(1)上記スパッタリング装置のターゲット設置冶具に上記第1の有機化合物のターゲットを装着する工程;
(2)上記スパッタリング装置のスパッタ室内を第1の所定の圧力に減圧する工程;
(3)スパッタガスと上記第2の有機化合物の気体との混合気体を、上記スパッタリング装置のスパッタ室内に、該スパッタ室内が前記第1の所定の圧力以上である第2の所定の圧力となるように導入する工程;及び、
(4)上記第1の有機化合物のターゲットに電力を投入し、スパッタリングすることにより、基材の面の上に上記複合膜を形成する工程
を含む、上記製造方法。
[2].
上記スパッタリング装置が、ロール・トゥ・ロール方式のスパッタリング装置である、[1]項に記載の製造方法。
[3].
上記混合気体の混合比(上記スパッタガスの体積/上記第2の有機化合物の気体の体積:標準状態(0℃及び1気圧)換算)が、60/40~99.999/0.001である、[1]項又は[2]項に記載の製造方法。
[4].
上記第2の有機化合物の気体が、飽和炭化水素の1個又は2個以上の水素原子が弗素原子に置換された構造を有する化合物であって標準状態(温度25℃、圧力100KPa)で気体の化合物、及び不飽和炭化水素の1個又は2個以上の水素原子が弗素原子に置換された構造を有する化合物であって標準状態(温度25℃、圧力100KPa)で気体の化合物からなる群から選択される1種以上の化合物の気体を含む、[1]~[3]の何れか1項に記載の製造方法。
[5].
上記第1の有機化合物のターゲットが、シリコーン樹脂を含む、[1]~[4]の何れか1項に記載の製造方法。
上記(A-1)の替りに上記(A-3)を用いたこと以外は、例1と同様にスパッタ膜を形成した。このとき成膜時間は30分間であり、該スパッタ膜の厚みは200nmとなる成膜条件であった。上記スパッタ膜をFT-IRの正反射法で分析したところ、C-F結合に由来するピークが現れていた。このことから、テトラフルオロメタンに由来する弗素原子がシリコーン樹脂を変性していること、即ち、複合膜が形成されたことを確認した。
2:繰り出しロール
3、3’:移送ロール
4:スパッタロール
5:巻き取りロール
6:スパッタガス導入口
7:排気口
8、8’:ターゲット設置冶具
9、9’:ターゲット
10:フィルム基材
11:積層体
12、12’:フィルムロール
13:防着板
14:防着板取付冶具
15、15’:ターゲット設置冶具
16、16’:ターゲット
17、17’:シャッター
18:スパッタテーブル
19:基材
20:スパッタ室
21:排気口
22:スパッタガス導入口
Claims (12)
- 複合膜の製造方法であって、
スパッタリング装置を使用し、
(A)標準状態(温度25℃、圧力100KPa)で固体の物質のターゲット、及び
(B)スパッタガスとの混合気体を調製可能な物質の気体を用い、
(1)上記スパッタリング装置のターゲット設置冶具に上記(A)ターゲットを装着する工程;
(2)上記スパッタリング装置のスパッタ室内を第1の所定の圧力に減圧する工程;
(3)スパッタガスと上記(B)気体との混合気体を、上記スパッタリング装置のスパッタ室内に、該スパッタ室内が前記第1の所定の圧力以上である第2の所定の圧力となるように導入する工程;及び、
(4)上記(A)ターゲットに電力を投入し、スパッタリングすることにより、基材の面の上に上記複合膜を形成する工程
を含む、上記製造方法。 - 上記スパッタリング装置が、ロール・トゥ・ロール方式のスパッタリング装置である、請求項1に記載の製造方法。
- 上記混合気体の混合比(上記スパッタガスの体積/上記(B)気体の体積)が、60/40~99.999/0.001である、請求項1に記載の製造方法。
- 上記(B)気体が有機化合物の気体を含む、請求項1に記載の製造方法。
- 上記有機化合物の気体が、飽和炭化水素の1個又は2個以上の水素原子が弗素原子に置換された構造を有する化合物であって標準状態で気体の化合物、及び不飽和炭化水素の1個又は2個以上の水素原子が弗素原子に置換された構造を有する化合物であって標準状態で気体の化合物からなる群から選択される1種以上の化合物の気体を含む、請求項4に記載の製造方法。
- 上記(A)ターゲットが無機物質のターゲットである、請求項1~5の何れか1項に記載の製造方法。
- 上記無機物質のターゲットが、2.6~3.7eVのバンドギャップを有する無機物質を含む、請求項6に記載の製造方法。
- 上記無機物質のターゲットが酸化セリウムを含む、請求項6に記載の製造方法。
- 上記スパッタリング装置が、ロール・トゥ・ロール方式のスパッタリング装置であり;
上記混合気体の混合比(上記スパッタガスの体積/上記(B)気体の体積)が、60/40~99.999/0.001であり;
上記(B)気体が有機化合物の気体を含み;
上記有機化合物の気体が、飽和炭化水素の1個又は2個以上の水素原子が弗素原子に置換された構造を有する化合物であって標準状態で気体の化合物、及び不飽和炭化水素の1個又は2個以上の水素原子が弗素原子に置換された構造を有する化合物であって標準状態で気体の化合物からなる群から選択される1種以上の化合物の気体を含み;
上記(A)ターゲットが無機物質のターゲットであり;
上記無機物質のターゲットが2.6~3.7eVのバンドギャップを有する無機物質を含み;
上記無機物質のターゲットが酸化セリウムを含む、
請求項1に記載の製造方法。 - 上記(A)ターゲットが有機化合物のターゲットである、請求項1~5の何れか1項に記載の製造方法。
- 上記有機化合物のターゲットがシリコーン樹脂を含む、請求項10に記載の製造方法。
- 上記スパッタリング装置が、ロール・トゥ・ロール方式のスパッタリング装置であり;
上記混合気体の混合比(上記スパッタガスの体積/上記(B)気体の体積)が、60/40~99.999/0.001であり;
上記(B)気体が有機化合物の気体を含み;
上記有機化合物の気体が、飽和炭化水素の1個又は2個以上の水素原子が弗素原子に置換された構造を有する化合物であって標準状態で気体の化合物、及び不飽和炭化水素の1個又は2個以上の水素原子が弗素原子に置換された構造を有する化合物であって標準状態で気体の化合物からなる群から選択される1種以上の化合物の気体を含み;
上記(A)ターゲットが有機化合物のターゲットであり;
上記有機化合物のターゲットがシリコーン樹脂を含む、請求項1に記載の製造方法。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07166344A (ja) * | 1993-12-10 | 1995-06-27 | Olympus Optical Co Ltd | 金属フッ化物薄膜の成膜方法 |
JPH08211201A (ja) * | 1995-02-02 | 1996-08-20 | Olympus Optical Co Ltd | 光学薄膜およびその製造方法 |
JP2019059027A (ja) * | 2017-09-25 | 2019-04-18 | 東レ株式会社 | 親水性と撥油性が求められる用途の積層体とその製造方法 |
WO2019142830A1 (ja) * | 2018-01-18 | 2019-07-25 | 株式会社表面・界面工房 | 有機無機ハイブリッド膜 |
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- 2022-05-25 EP EP22815929.9A patent/EP4350027A1/en active Pending
- 2022-05-25 WO PCT/JP2022/021334 patent/WO2022255179A1/ja active Application Filing
- 2022-05-31 TW TW111120147A patent/TW202248164A/zh unknown
- 2022-06-03 JP JP2022090550A patent/JP2022186664A/ja active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07166344A (ja) * | 1993-12-10 | 1995-06-27 | Olympus Optical Co Ltd | 金属フッ化物薄膜の成膜方法 |
JPH08211201A (ja) * | 1995-02-02 | 1996-08-20 | Olympus Optical Co Ltd | 光学薄膜およびその製造方法 |
JP2019059027A (ja) * | 2017-09-25 | 2019-04-18 | 東レ株式会社 | 親水性と撥油性が求められる用途の積層体とその製造方法 |
WO2019142830A1 (ja) * | 2018-01-18 | 2019-07-25 | 株式会社表面・界面工房 | 有機無機ハイブリッド膜 |
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