Method for manufacturing composite film and method for manufacturing organic-inorganic hybrid film

Abstract

To provide a method for manufacturing a new composite film.SOLUTION: A method for manufacturing a composite film comprises the steps of: (1) using a sputtering apparatus and mounting (A) a target on the target placement tool of the sputtering apparatus using (A) the target of a material solid in a normal state and (B) the gas of a material capable of preparing mixed gas with sputtering gas; (2) reducing the inside of the sputtering chamber of the sputtering apparatus into a predetermined pressure; (3) introducing the mixed gas of the sputtering gas with (B) the gas into the inside of the sputtering chamber of the sputtering apparatus so that the inside of the sputtering chamber has a predetermined pressure; and (4) supplying electric power to (A) the target to form the composite film on the surface of a base material by sputtering.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a method for producing a composite film and a method for producing an organic-inorganic hybrid film. [Background technology]

[0002] Traditionally, inorganic glass has been used as a base material for automobile windows and windshields, building windows and doors, and protective panels and display panels for image display devices, due to its excellent chemical stability and ability to meet required characteristics such as transparency, rigidity, scratch resistance, and weather resistance. However, inorganic glass has problems such as low impact resistance and brittleness, poor processability, difficulty in handling, high specific gravity and weight, and difficulty in meeting the requirements for curved and flexible products. For this reason, alternative materials to glass have been actively researched, and transparent resin laminates have been proposed, which consist of a sheet or plate of transparent resin such as polycarbonate resin or acrylic resin laminated with a hard coat (for example, Patent Documents 1 and 2). However, their weather resistance and stain resistance, especially weather resistance, are insufficient for applications in environments exposed to ultraviolet light.

[0003] Therefore, the applicant proposed forming an organic-inorganic hybrid film of cerium oxide and an organofluorine compound on the surface of a transparent resin laminate, and proposed a method for manufacturing the organic-inorganic hybrid film using a sputtering apparatus capable of performing two-pole sputtering, using an organic material target and an inorganic material target, and a method for manufacturing the film using a target made of a mixture of organic and inorganic materials (Patent Document 3). However, when attempting to form an organic-inorganic hybrid film productively using a roll-to-roll method, the specifications of the two-pole sputtering apparatus become complex, resulting in the handling and setting of the apparatus becoming critical, making it difficult to form an organic-inorganic hybrid film with stable industrial quality (such as film thickness and compositional uniformity); and it was found that the methods and conditions suitable for manufacturing targets differ greatly between organic and inorganic materials, and that it is difficult to industrially produce targets made of a mixture of organic and inorganic materials. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2014-043101 [Patent Document 2] Japanese Patent Publication No. 2014-040017 [Patent Document 3] Japanese Patent Publication No. 2019-123872 [Patent Document 4] Japanese Patent Publication No. 2001-100008 [Patent Document 5] Special Publication No. 03-014043 [Overview of the project] [Problems that the invention aims to solve]

[0005] An object of the present invention is to provide a novel method for manufacturing composite films. A further object of the present invention is to provide a novel method for manufacturing organic-inorganic hybrid films. [Means for solving the problem]

[0006] As a result of diligent research, the inventors have found that the above problem can be solved by a specific manufacturing method.

[0007] In other words, the embodiments of the present invention are as follows. [1]. A method for manufacturing a composite film, Using a sputtering device, (A) A target of a solid material under standard conditions (temperature 25°C, pressure 100kPa) (B) Using a gas of a substance capable of preparing a mixed gas with sputtering gas, (1) The step of mounting the target (A) on the target mounting jig of the sputtering apparatus; (2) A step of reducing the pressure inside the sputtering chamber of the sputtering apparatus to a predetermined pressure; (3) A step of introducing a mixture of sputtering gas and the gas (B) above into the sputtering chamber of the sputtering apparatus so that the pressure inside the sputtering chamber reaches a predetermined level; and, (4) A step of applying power to the target (A) above and forming the composite film on the surface of the substrate by sputtering; The above manufacturing method, including the above. [2]. The manufacturing method described in item [1], wherein the sputtering apparatus is a roll-to-roll sputtering apparatus. [3]. The manufacturing method according to item [1] or [2], wherein the mixing ratio of the above-mentioned mixed gas (volume of the above-mentioned sputtering gas / volume of the above-mentioned (B) gas) is 60 / 40 to 99.999 / 0.001. [4]. The manufacturing method described in any one of items [1] to [3] above, wherein the gas (B) contains an organic compound gas. [5]. The gas of the above 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 a gaseous compound under standard conditions (temperature 25 °C, pressure 100 KPa), and a compound having a structure in which one or more hydrogen atoms of an unsaturated hydrocarbon are substituted with fluorine atoms and is a gaseous compound under standard conditions (temperature 25 °C, pressure 100 KPa), and the manufacturing method according to item [4], which contains the gas of one or more compounds selected from the group consisting of such compounds. [6]. The manufacturing method according to any one of items [1] to [5], wherein the target (A) is a target of an inorganic substance. [7]. The manufacturing method according to item [6], wherein the target of the inorganic substance contains an inorganic substance having a band gap of 2.6 to 3.7 eV. [8]. The manufacturing method according to item [6] or [7], wherein the target of the inorganic substance contains cerium oxide. [9]. The above sputtering apparatus is a roll-to-roll type sputtering apparatus; The mixing ratio of the above mixed gas (volume of the above sputtering gas / volume of the above gas (B)) is 60 / 40 to 99.999 / 0.001; The above gas (B) contains the gas of an organic compound; The gas of the above 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 a gaseous compound under standard conditions (temperature 25 °C, pressure 100 KPa), and a compound having a structure in which one or more hydrogen atoms of an unsaturated hydrocarbon are substituted with fluorine atoms and is a gaseous compound under standard conditions (temperature 25 °C, pressure 100 KPa), and contains the gas of one or more compounds selected from the group consisting of such compounds; The above target (A) is a target of an inorganic substance; The above target of the inorganic substance contains an inorganic substance having a band gap of 2.6 to 3.7 eV; The manufacturing method according to item [1], wherein the above target of the inorganic substance contains cerium oxide.

[10] . The production method according to any one of [1] to [5], wherein the target in (A) is a target of an organic compound.

[11] . The production method according to

[10] , wherein the target of the organic compound contains a silicon resin.

[12] . The sputtering device is a roll-to-roll sputtering device; The mixing ratio of the mixed gas (volume of the sputtering gas / volume of the gas in (B)) is 60 / 40 to 99.999 / 0.001; The gas in (B) contains a gas of an organic compound; The gas of the 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 a gas compound under standard conditions (temperature 25°C, pressure 100 KPa), and a compound having a structure in which one or more hydrogen atoms of an unsaturated hydrocarbon are substituted with fluorine atoms and is a gas compound under standard conditions (temperature 25°C, pressure 100 KPa), and contains a gas of one or more compounds selected from the group consisting of such compounds. The target in (A) is a target of an organic compound; The production method according to [1], wherein the target of the organic compound contains a silicon resin.

[0008] Aspects of the production method of the organic-inorganic hybrid film of the present invention are as follows. [1]. A production method of an organic-inorganic hybrid film, using a sputtering device, using a target of an inorganic substance and a gas of an organic compound, (1) A step of mounting the target of the inorganic substance on a target mounting jig of the sputtering device; (2) A step of reducing the pressure in the sputtering chamber of the sputtering device to a predetermined pressure; (3) A step of introducing a mixed gas of a sputtering gas and a gas of the organic compound into the sputtering chamber of the sputtering device so that the sputtering chamber has a predetermined pressure; and, (4) A step of forming the organic-inorganic hybrid film on the surface of a substrate by applying power to the inorganic target and sputtering it; The above manufacturing method, including the above. [2]. The manufacturing method described in item [1], wherein the sputtering apparatus is a roll-to-roll sputtering apparatus. [3]. The manufacturing method according to item [1] or [2], wherein the mixing ratio of the above mixed gas (volume of the above sputtered gas / volume of the above organic compound gas) is 60 / 40 to 99.999 / 0.001. [4]. A method for producing the above-mentioned organic compound gas, comprising one or more compounds selected from the group consisting of compounds having a structure in which one or more hydrogen atoms of a saturated hydrocarbon are replaced by fluorine atoms and are gaseous under standard conditions (temperature 25°C, pressure 100kPa), and compounds having a structure in which one or more hydrogen atoms of an unsaturated hydrocarbon are replaced by fluorine atoms and are gaseous under standard conditions (temperature 25°C, pressure 100kPa), according to any one of items [1] to [3]. [5]. The manufacturing method according to any one of items [1] to [4], wherein the target of the above-mentioned inorganic substance comprises an inorganic substance having a band gap of 2.6 to 3.7 eV. [6]. A method for producing the inorganic substance according to any one of items [1] to [5], wherein the target of the inorganic substance contains cerium oxide. [Effects of the Invention]

[0009] The present invention fundamentally solves the problem that arises when attempting to form composite films productively using a roll-to-roll method, where two-pole sputtering equipment has complex specifications, resulting in difficult handling and setting of the equipment, and making it difficult to form composite films with stable industrial quality (such as uniformity of film thickness and composition). Therefore, it is suitable as a method for manufacturing composite films, especially when attempting to form composite films productively using a roll-to-roll method.

[0010] The present invention fundamentally solves the problems of producing organic-inorganic hybrid films, particularly when attempting to form organic-inorganic hybrid films productively using a roll-to-roll method. These problems include the complexity of the specifications of two-pole sputtering equipment, the resulting difficulty in handling and setting up the equipment, and the difficulty in industrially producing organic-inorganic hybrid films with stable quality (such as film thickness and compositional uniformity); and the significant differences in suitable methods and conditions for target production between organic and inorganic materials, making it difficult to industrially produce targets made from mixtures of organic and inorganic materials. Therefore, the present invention is suitable as a method for producing organic-inorganic hybrid films, especially when attempting to form organic-inorganic hybrid films productively using a roll-to-roll method. [Modes for carrying out the invention]

[0011] In this specification, the term "inorganic substance" is used to include mixtures containing two or more inorganic substances. The term "organic compound" is used to include mixtures containing two or more organic compounds. The term "resin" is used to include resin mixtures containing two or more resins, and resin compositions containing components other than resins.

[0012] In this specification, the term "film" is used interchangeably or interchangeably with the term "sheet." In this specification, the terms "film" and "sheet" are used for materials that can be industrially wound into rolls. The term "plate" is used for materials that cannot be industrially wound into rolls. In this specification, lamination of one layer with another includes both directly laminating those layers and laminating them with one or more other layers, such as an anchor coat, interposed between them.

[0013] In this specification, the term "greater than or equal to" in relation to a numerical range means a certain number or greater than a certain number. For example, "20% or more" means 20% or greater than 20%. The term "less than or equal to" in relation to a numerical range means a certain number or less than a certain number. For example, "20% or less" means 20% or less than 20%. The symbol "~" in relation to a numerical range means a certain number, greater than a certain number and less than another certain number, or another certain number. Here, the other certain number is a number greater than a certain number. For example, "10~90%" means 10%, greater than 10% and less than 90%, or 90%. Furthermore, the upper and lower limits of a numerical range can be combined arbitrarily, and embodiments with such arbitrary combinations should be discernible. For example, from descriptions relating to the numerical range of a certain characteristic, such as "usually 10% or more, preferably 20% or more. On the other hand, usually 40% or less, preferably 30% or less," or "usually 10-40%, preferably 20-30%," it can be inferred that, in one embodiment, the numerical range of that characteristic is 10-40%, 20-30%, 10-30%, or 20-40%.

[0014] Except in the examples, or unless otherwise specified, all numerical values ​​used herein and in the claims should be understood to be modified by the term “approximately.” Without attempting to limit the application of the doctrine of equivalents to the claims, each numerical value should be interpreted in terms of significant figures and by applying common rounding methods.

[0015] In this specification, terms used to specify shapes or geometric conditions, such as parallel, orthogonal, and perpendicular, shall include not only their strict meanings but also substantially equivalent conditions.

[0016] In this specification, "composite membrane" means a membrane containing atoms derived from two or more different substances. In this specification, "organic-inorganic hybrid membrane" means a membrane containing atoms derived from an inorganic substance and atoms derived from an organic compound.

[0017] The method for producing the composite film of the present invention is as follows: Using a sputtering device, (A) A target of a solid material under standard conditions (temperature 25°C, pressure 100kPa) (B) Using a gas of a substance capable of preparing a mixed gas with sputtering gas, (1) The step of mounting the target (A) on the target mounting jig of the sputtering apparatus; (2) A step of reducing the pressure inside the sputtering chamber of the sputtering apparatus to a predetermined pressure; (3) A step of introducing a mixture of sputtering gas and the gas (B) above into the sputtering chamber of the sputtering apparatus so that the pressure inside the sputtering chamber reaches a predetermined level; and, (4) A step of applying power to the target (A) above and forming the composite film on the surface of the substrate by sputtering; Includes.

[0018] The composite film formed by the method for manufacturing the composite film of the present invention contains (A) atoms derived from a solid substance under standard conditions (temperature 25°C, pressure 100 kPa) and (B) atoms derived from a substance capable of preparing a mixed gas with sputtering gas.

[0019] In a typical embodiment, the composite film formed by the method for manufacturing a composite film of the present invention may contain (A) atoms derived from a solid substance under standard conditions (temperature 25°C, pressure 100kPa) and (B) atoms derived from a substance capable of preparing a mixed gas with sputtering gas, and may also contain the other substance (usually considered to be a solid substance under standard conditions (temperature 25°C, pressure 100kPa)) modified by one of the substances (usually considered to be (B) a substance capable of preparing a mixed gas with sputtering gas).

[0020] The method for manufacturing a composite film of the present invention will be described below, primarily using the case of a composite film manufacturing method of the present invention that is an organic-inorganic hybrid film as an example. When manufacturing a composite film other than an organic-inorganic hybrid film, it goes without saying that the method for manufacturing a composite film of the present invention can be carried out by appropriately substituting "organic-inorganic hybrid film" with "composite film," "target of an inorganic compound" with "(A) a target of a substance that is solid under standard conditions (temperature 25°C, pressure 100kPa)," and "gas of an organic compound" with "(B) a gas of a substance that can be prepared as a mixed gas with sputtering gas."

[0021] 1. Sputtering equipment: The present invention provides a method for manufacturing a composite film using a sputtering apparatus. The present invention also provides a method for manufacturing an organic-inorganic hybrid film using a sputtering apparatus. The sputtering apparatus is not particularly limited, and any known sputtering apparatus can be used. As the sputtering apparatus, from the viewpoint of forming an organic-inorganic hybrid film with good productivity, a sputtering apparatus having a mechanism for unwinding a film substrate from a film roll, forming an organic-inorganic hybrid film on the surface of the film substrate, and then winding it up as a film roll (hereinafter sometimes referred to as a "roll-to-roll sputtering apparatus") is preferred.

[0022] Figure 1 is a conceptual diagram showing an example of a roll-to-roll sputtering apparatus. The roll-to-roll sputtering apparatus will be described below with reference to Figure 1 as appropriate. The apparatus in Figure 1 has a feed roll 2, a transfer roll 3, a sputtering roll 4, a transfer roll 3', and a winding roll 5 in the sputtering chamber 1. These allow the film substrate 10 to be fed from the film roll 12, an organic-inorganic hybrid film (not shown) to be formed on the surface of the film substrate 10, and then the laminate 11 having the organic-inorganic hybrid film (not shown) on the surface of the film substrate 10 to be wound up as a film roll 12'.

[0023] As a roll-to-roll sputtering apparatus, an apparatus having two or more sputtering rolls may be used. This allows for easy installation of two or more target mounting jigs, thereby increasing the film deposition speed and line speed (productivity) by using two or more targets. Furthermore, by forming an anchor film (a film that functions as an anchor to increase the interlayer adhesion strength between the film substrate and the organic-inorganic hybrid film) on the surface of the film substrate with the first sputtering roll, and then forming the organic-inorganic hybrid film on the surface of the anchor film with the second and subsequent sputtering rolls, a laminate having the film substrate, the anchor film, and the organic-inorganic hybrid film can be obtained in a single pass.

[0024] The sputtering chamber 1 has a sputtering gas inlet 6, allowing gas to be introduced into the sputtering chamber 1 through the sputtering gas inlet 6.

[0025] The sputtering chamber 1 has an exhaust port 7, and can be exhausted from the exhaust port 7 using an exhaust device (not shown) to maintain a predetermined pressure. The exhaust device is not particularly limited as long as it has the capacity to maintain the predetermined pressure. Examples of such exhaust devices include positive displacement vacuum pumps such as oil rotary pumps, momentum transport vacuum pumps such as turbomolecular pumps, gas storage vacuum pumps such as cryopumps, and combinations thereof.

[0026] The apparatus shown in Figure 1 has two target mounting fixtures 8 and 8', each capable of mounting one target 9 and 9' (a total of two targets). Separate impedance matching devices (not shown) and high-frequency power supplies (not shown) are connected to the targets 9 and 9' mounted on the target mounting fixtures 8 and 8', respectively, allowing for individual control of the power supplied to the targets 9 and 9' to adjust the film deposition conditions as needed. Furthermore, the target mounting fixtures 8 and 8' are equipped with internal channels for a medium such as water, enabling the temperature of the targets 9 and 9' to be controlled to a predetermined temperature.

[0027] The targets 9 and 9', mounted on the target mounting jigs 8 and 8', are positioned opposite the spatter roll 4. The distance between target 9 and the spatter roll 4 (the distance between target 9' and the spatter roll 4) is not particularly limited, but is usually 1 to 20 cm, preferably 3 to 15 cm, and more preferably 5 to 12 cm.

[0028] 2. (A) Targets of substances that are solid under standard conditions: The present invention provides a method for producing a composite film using (A) a target material that is solid under standard conditions (temperature 25°C, pressure 100kPa). That is, the composite film produced by the present invention provides a method for producing a composite film that contains atoms derived from the above-mentioned (A) material that is solid under standard conditions (temperature 25°C, pressure 100kPa).

[0029] The substance (A) described above is not particularly limited, except that it is a substance that can stably maintain a solid state under standard conditions (temperature 25°C, pressure 100kPa), and preferably a substance that can stably maintain a solid state under standard conditions (temperature 25°C, pressure 100kPa) and at the pressure and temperature in each step of forming the composite film.

[0030] The substance (A) described above may be an inorganic substance or an organic compound.

[0031] In one preferred embodiment, the substance (A) described above may be a silicone resin. The silicone resin is a polymer compound having a siloxane bond (Si-O-Si) as its main backbone. Examples of the silicone resin include polydimethylsiloxane, polydiethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane, as well as modified versions thereof. One or more of these can be used as the silicone resin.

[0032] The substance (A) described above is a substance that can stably maintain a solid state under standard conditions (temperature 25°C, pressure 100kPa), preferably a substance that can stably maintain a solid state under standard conditions (temperature 25°C, pressure 100kPa) and at the pressure and temperature during each step of forming the composite film. This can be appropriately selected from among such substances, taking into account the characteristics and functions to be imparted to the composite film.

[0033] From the viewpoint of ease of handling, it is preferable to mold the above-mentioned substance (A) by a known method and use the molded body as a target. If the above-mentioned substance (A) is an inorganic substance, the method may include sintering. If the above-mentioned substance (A) is an organic compound, the method may include injection molding, casting solidification, etc. The shape of the target of the above-mentioned substance (A) can be appropriately selected from the viewpoint of ensuring that the thickness of the composite film is uniform, taking into consideration the specifications of the sputtering apparatus used.

[0034] 2-1. Inorganic substance targets: The present invention provides a method for producing an organic-inorganic hybrid film using an inorganic target. That is, the organic-inorganic hybrid film produced by the present invention's method for producing an organic-inorganic hybrid film contains atoms derived from the inorganic substance.

[0035] The inorganic substance is not particularly limited, except that it is an inorganic substance that can stably maintain a solid state under standard conditions (temperature 25°C, pressure 100kPa), and preferably an inorganic substance that can stably maintain a solid state under standard conditions (temperature 25°C, pressure 100kPa) and at the pressure and temperature in each step of forming the organic-inorganic hybrid film.

[0036] The inorganic substance can be appropriately selected from among inorganic substances that can stably maintain a solid state under standard conditions (temperature 25°C, pressure 100kPa), preferably under standard conditions (temperature 25°C, pressure 100kPa) and under the pressure and temperature at each step in forming the organic-inorganic hybrid film, taking into consideration the characteristics and functions to be imparted to the organic-inorganic hybrid film.

[0037] When attempting to impart a low ultraviolet transmittance to the above-mentioned organic-inorganic hybrid film, the inorganic substance used can be one in which the band gap is typically 3.7 eV or less, preferably 3.6 eV or less, more preferably 3.5 eV or less, even more preferably 3.4 eV or less, even more preferably 3.3 eV or less, and most preferably 3.25 eV or less, from the viewpoint of sufficiently lowering the transmittance of ultraviolet light having an energy greater than or equal to the energy of the carbon-carbon bond of the organic compound (3.82 eV), and furthermore preferably sufficiently lowering the transmittance of ultraviolet light with a wavelength of 380 nm (energy of 3.26 eV).

[0038] When attempting to impart high visible light transmittance to the above organic-inorganic hybrid film, the inorganic substance used can be one in which, from the viewpoint of sufficiently transmitting visible light with a wavelength of 490 nm or more (the energy of visible light with a wavelength of 490 nm is 2.53 eV), and further from the viewpoint of sufficiently transmitting visible light with a wavelength of 400 nm or more (the energy of visible light with a wavelength of 400 nm is 3.10 eV), the inorganic substance has a band gap of typically 2.6 eV or more, preferably 2.7 eV or more, more preferably 2.8 eV or more, even more preferably 2.9 eV or more, even more preferably 3.0 eV or more, even more preferably 3.1 eV or more, and most preferably 3.15 eV or more.

[0039] Here, the band gap 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. When a photon is incident on a material with a band gap smaller than the photon's energy, there is a high probability that the photon will excite electrons and reflect the photon. On the other hand, when a photon is incident on a material with a band gap larger than the photon's energy, there is a high probability that the photon will pass through without exciting electrons. Although we do not intend to be bound by theory, it is thought that by using an inorganic material with a band gap smaller than the energy of ultraviolet light and larger than the energy of visible light, it is possible to form an organic-inorganic hybrid film with low ultraviolet transmittance and high visible light transmittance.

[0040] Examples of inorganic substances used to impart low ultraviolet transmittance and high visible light transmittance to the above-mentioned organic-inorganic hybrid film include cerium dioxide (3.2 eV), cerium oxide such as diserium 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). The values ​​in parentheses are the band gaps. Among these, cerium dioxide, cerium oxide such as diserium trioxide, and anatase-type titanium dioxide are preferred, and cerium dioxide is more preferred.

[0041] As the inorganic substances mentioned above, one or a mixture of two or more of these can be used.

[0042] From the viewpoint of ease of handling, it is preferable to pre-form the inorganic material by known methods such as sintering and use a molded body such as a sintered body as a target. The shape of the target of the inorganic material (molded body such as a sintered body) can be appropriately selected from the viewpoint of ensuring that the thickness of the organic-inorganic hybrid film is uniform, taking into consideration the specifications of the sputtering apparatus used.

[0043] When using a roll-to-roll sputtering apparatus as described above, the shape of the inorganic material target can be appropriately selected considering the specifications (width, diameter) of the sputtering roll positioned opposite the target, the distance between the target and the sputtering roll, the width of the film substrate 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 laminate as a product). This selection is made with the aim of ensuring uniformity in the film thickness and composition of the organic-inorganic hybrid film within the effective width of the laminate, particularly from the viewpoint of preventing lateral fluctuations in the film thickness and composition, and from the viewpoint of suppressing contamination of the sputtering roll.

[0044] When a roll-to-roll sputtering apparatus is used as the sputtering apparatus described above, the shape of the inorganic material target may be a rectangular parallelepiped. The length of the horizontal plane of the rectangular parallelepiped (the length of the side corresponding to the width direction of the sputtering roll when the sputtering roll is positioned opposite the rectangular parallelepiped on the vertical and horizontal planes of the rectangular parallelepiped) is usually a length greater than or equal to the effective width of the laminate, preferably a length greater than or equal to the width of the film substrate, and more preferably a length greater than or equal to the width of the film substrate + 3 cm, from the viewpoint of improving the uniformity of the film thickness and composition of the organic-inorganic hybrid film and widening the effective width of the laminate.

[0045] One preferred embodiment is to provide a protective plate between the target and the sputtering roll, shaped to mask the sides of the sputtering roll, at positions opposite each of the sides of the sputtering roll, from the viewpoint of suppressing contamination of the sputtering roll. Here, "sides of the sputtering roll" refers to the exposed portion of the sputtering roll on the side of the portion covered by the film substrate when the sputtering roll is fitted with the film substrate. Figure 2 is a photograph showing an example of a roll-to-roll sputtering apparatus with protective plates. In the apparatus of Figure 2, protective plates 13 shaped to mask the sides of the sputtering roll 4 are attached by a protective plate mounting jig 14 at a position opposite to the sides of the sputtering roll 4. The target of the inorganic material is then installed facing the sputtering roll 4 in the space composed of the protective plates 13, the protective plate mounting jig 14, the protective plate on the opposite side from the side shown in the photograph, and the protective plate mounting jig on the opposite side from the side shown in the photograph.

[0046] The shape of the target of the inorganic material may be, for example, a rectangular parallelepiped with a vertical length of typically 1 to 30 cm, preferably 5 to 20 cm, a horizontal length of typically 40 to 60 cm, preferably 53 to 58 cm, and a height of typically 0.1 to 5 cm, preferably 0.2 to 2 cm, when the sputter roll is 70 cm wide and 40 cm in diameter, the distance between the target and the sputter roll is 8 cm, the width of the film substrate is 50 cm, and the effective width of the laminate is 40 cm.

[0047] 3. (B) Gases of substances that can be prepared as a mixed gas with sputtered gas: The present invention's method for producing a composite film uses a gas of a substance capable of preparing a mixed gas with (B) a sputtering gas. That is, the composite film produced by the present invention's method for producing a composite film contains atoms derived from the substance capable of preparing a mixed gas with the sputtering gas.

[0048] The present invention's method for manufacturing a composite film uses a gas as one of the materials forming the composite film, and does not use a target. Therefore, the inconvenience of using a two-pole sputtering apparatus when attempting to form a composite film productively using a roll-to-roll method, where the specifications are complex and the handling and setting of the apparatus are difficult, making it difficult to form a composite film with stable industrial quality (such as thickness and compositional uniformity), is fundamentally resolved.

[0049] The substance capable of preparing a mixed gas with the sputtering gas described above (B) is not particularly limited, other than being a substance capable of preparing a mixed gas with the sputtering gas, that is, a substance that can stably maintain a gaseous state at the pressure and temperature in each step of forming the composite film. The substance capable of preparing a mixed gas with the sputtering gas described above (B) is not limited to a substance that is a gas at standard conditions (temperature 25°C, pressure 100kPa). The substance capable of preparing a mixed gas with the sputtering gas described above (B) may be a substance that becomes a gas by heating (usually below the upper limit temperature at which the film substrate can be actually used) and / or by reducing the pressure. From the viewpoint of workability when mixing the sputtering gas described above and the gaseous substance capable of preparing a mixed gas with the sputtering gas described above (B) to prepare the mixed gas, the substance capable of preparing a mixed gas with the sputtering gas described above (B) may preferably be a substance that is a gas at standard conditions (temperature 25°C, pressure 100kPa).

[0050] The substance capable of preparing the mixed gas with the sputtered gas described above (B) may be an organic compound or an inorganic substance.

[0051] The substance capable of preparing the mixed gas with the sputtering gas described in (B) above can be appropriately selected from among substances that can stably maintain a gaseous state at the pressure and temperature in each step of forming the composite film, taking into consideration the characteristics and functions to be imparted to the composite film.

[0052] 3-1. Gases of organic compounds: The present invention provides a method for producing an organic-inorganic hybrid membrane using a gaseous organic compound. That is, the organic-inorganic hybrid membrane produced by the present invention's method for producing an organic-inorganic hybrid membrane contains atoms derived from the gaseous organic compound.

[0053] The present invention's method for manufacturing organic-inorganic hybrid films uses a gas as the organic compound and does not use an organic compound target (a molded body as a target for the organic compound). Therefore, when attempting to form organic-inorganic hybrid films productively using a roll-to-roll method, the specifications of the two-pole sputtering apparatus become complex, resulting in demanding handling and setting of the apparatus, making it difficult to form organic-inorganic hybrid films with stable industrial quality (such as film thickness and compositional uniformity). Furthermore, the methods and conditions suitable for manufacturing targets differ greatly between organic and inorganic materials, making it difficult to industrially produce targets made from mixtures of organic and inorganic materials. Both of these inconveniences are fundamentally resolved.

[0054] The above organic compound is not particularly limited, except that it is an organic compound that can stably maintain a gaseous state at the pressure and temperature in each step of forming the above organic-inorganic hybrid film. The above organic compound is not limited to an organic compound that is a gas at standard conditions (temperature 25°C, pressure 100kPa). The above organic compound may be an organic compound that becomes a gas upon heating (usually below the upper limit temperature at which the above film substrate can be used) and / or reduced pressure. From the viewpoint of workability when mixing the above sputtering gas and the gaseous organic compound to prepare the mixed gas, the above organic compound may preferably be an organic compound that is a gas at standard conditions (temperature 25°C, pressure 100kPa).

[0055] The above organic compounds can be appropriately selected from among organic compounds that can stably maintain a gaseous state at the pressure and temperature during each step of forming the above organic-inorganic hybrid film, taking into consideration the characteristics and functions to be imparted to the organic-inorganic hybrid film.

[0056] Examples of organic compounds used to impart water-repellent and anti-fouling properties to the above-mentioned organic-inorganic hybrid film include organofluorine compounds. These organofluorine compounds are compounds having a fluorine-carbon bond, and are typically compounds having a structure in which one or more hydrogen atoms of an organic compound such as a hydrocarbon are replaced by fluorine atoms. The organofluorine compounds may preferably be gaseous organic compounds under standard conditions (temperature 25°C, pressure 100 kPa).

[0057] Examples of the above-mentioned organofluorine compounds include compounds having a structure in which one or more hydrogen atoms of saturated hydrocarbons such as tetrafluoromethane, trifluoromethane, difluoromethane, fluoromethane, and 1,1,1,2-tetrafluoroethane are replaced by fluorine atoms, and which are gases under standard conditions (temperature 25°C, pressure 100kPa); and compounds having a structure in which one or more hydrogen atoms of unsaturated hydrocarbons such as tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, hexafluoropropylene, pentafluoropropylene, tetrafluoropropylene, trifluoropropylene, and chlorotrifluoroethylene are replaced by fluorine atoms, and which are gases under standard conditions (temperature 25°C, pressure 100kPa).

[0058] As the above organic compounds, one or a mixture of two or more of these can be used.

[0059] 4.Base material: The present invention provides a method for manufacturing a composite film, in which the composite film is formed on at least one surface of a substrate. The substrate can be appropriately selected according to the application of the laminate or molded body having the composite film on at least one surface of the substrate (hereinafter, the term "laminated body" may simply refer to the laminate or molded body having the composite film on at least one surface of the substrate. Note that when simply referring to the laminate, this also includes the meaning of the laminate or molded body having the organic-inorganic hybrid film on at least one surface of the substrate). The present invention provides a method for manufacturing an organic-inorganic hybrid film, in which the organic-inorganic hybrid film is formed on at least one surface of a substrate. The substrate can be appropriately selected according to the application of the laminate or molded body having the organic-inorganic hybrid film on at least one surface of the substrate (hereinafter, the term "laminated body" may simply refer to the laminate or molded body having the organic-inorganic hybrid film on at least one surface of the substrate).

[0060] The composite film-forming surface of the above-mentioned substrate may be smooth or may have a three-dimensional shape such as irregularities. Here, "three-dimensional shape" means a shape that includes at least a part of a non-planar shape such as irregularities. The organic-inorganic hybrid film-forming surface of the above-mentioned substrate may be smooth or may have a three-dimensional shape such as irregularities. In one typical embodiment, the above-mentioned substrate is a film, a sheet, or a plate.

[0061] Examples of the above-mentioned substrates include inorganic glass films, inorganic glass sheets, or inorganic glass plates made of soda-lime glass, borosilicate glass, and quartz glass.

[0062] Examples of the above-mentioned substrates include resin films, resin sheets, or resin plates made from cellulose ester resins such as triacetylcellulose; polyester resins such as polyethylene terephthalate; cyclic hydrocarbon resins such as ethylene norbornene copolymers; acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, and vinylcyclohexane·(meth)acrylate copolymers; aromatic polycarbonate resins; polyolefin resins such as polypropylene and 4-methyl-pentene-1; polyamide resins; polyarylate resins; polymer-type urethane acrylate resins; and polyimide resins. These resin films include unoriented films, uniaxially oriented films, and biaxially oriented films. These resin films also include laminated resin films made by laminating one or more of these types in two or more layers. These resin sheets include unoriented sheets, uniaxially oriented sheets, and biaxially oriented sheets. These resin sheets also include laminated resin sheets made by laminating one or more of these types in two or more layers. These resin plates include laminated resin plates formed by stacking one or more of these types in two or more layers.

[0063] The above-mentioned substrate may be one having a functional layer on at least one of its surfaces. The surface on which the composite film is formed may be the surface on the functional layer side, or it may be the surface opposite to the functional layer. The above-mentioned substrate may be one having a functional layer on at least one of the resin film, resin sheet, or resin plate, and the surface on the functional layer side, or the surface opposite to the functional layer, may be used as the surface on which the organic-inorganic hybrid film is formed.

[0064] Examples of the functional layers mentioned above include those having functions such as hardness enhancement, anchoring, low refractive index, high refractive index, infrared shielding, infrared reflection, ultraviolet shielding, electromagnetic wave shielding, electromagnetic wave reflection, visibility control (blinding), and viewing angle control. The functional layers may be coating films (including hard coats) formed using paints, or films formed by dry coating methods such as sputtering, vacuum deposition, and chemical vapor deposition.

[0065] When inorganic glass is used as the substrate, the thickness of the inorganic glass film, inorganic glass sheet, or inorganic glass plate is not particularly limited and can be any thickness as desired. From the viewpoint of ease of handling of the laminate, it is usually 20 μm or more, preferably 50 μm or more. From the viewpoint of impact resistance of the inorganic glass, it is usually 0.8 mm or more, preferably 1 mm or more, and more preferably 1.5 mm or more. From the viewpoint of reducing the weight of the article using the laminate, it is usually 6 mm or less, preferably 4.5 mm or less, and more preferably 3 mm or less.

[0066] When resin is used as the base material, the thickness of the resin film, resin sheet, or resin plate is not particularly limited and can be any thickness as desired. From the viewpoint of ease of handling of the laminate, it is usually 20 μm or more, preferably 50 μm or more. When the laminate is used in applications that do not require high rigidity, from the viewpoint of economy, it is usually 250 μm or less, preferably 150 μm or less. When the laminate is used in applications that require high rigidity, from the viewpoint of maintaining rigidity, it is usually 300 μm or more, preferably 500 μm or more, more preferably 600 μm or more. Furthermore, from the viewpoint of meeting the demand for thinner articles using the laminate, it is usually 1500 μm or less, preferably 1200 μm or less, more preferably 1000 μm or less.

[0067] The above-mentioned substrate may be transparent, opaque, colored transparent, or colored opaque (having opacity). It can be appropriately selected considering the intended use of the laminate.

[0068] When attempting to impart high visible light transmittance to the above-mentioned organic-inorganic hybrid film, from the viewpoint of utilizing the high visible light transmittance of the organic-inorganic hybrid film, the visible light transmittance of the substrate may be 80% or higher, preferably 85% or higher, more preferably 88% or higher, even more preferably 90% or higher, and most preferably 92% or higher. In this case, the higher the visible light transmittance of the substrate, the better. Here, visible light transmittance is the ratio of the area obtained by integrating the transmission spectrum over the wavelength range of 400 to 780 nm to the area obtained by integrating the transmission spectrum over the wavelength range of 400 to 780 nm, assuming that the transmittance is 100% over the entire wavelength range of 400 to 780 nm. Visible light transmittance can be measured, for example, in accordance with JIS A5759:2008 6.4 Visible Light Transmittance Test, using a spectrophotometer "SolidSpec-3700 (product name)" from Shimadzu Corporation.

[0069] The thickness of the composite film can be appropriately selected considering the properties and functions to be imparted to the composite film and the application of the laminate. From the viewpoint of crack resistance, the thickness of the composite film may be typically 1 μm 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, from the viewpoint of reliably obtaining the properties and functions to be imparted by the composite film, the thickness may be typically 1 nm or more, preferably 10 nm or more, more preferably 20 nm or more, even more preferably 30 nm or more, and most preferably 40 nm or more.

[0070] The thickness of the above-mentioned organic-inorganic hybrid film can be appropriately selected considering the properties and functions to be imparted to the organic-inorganic hybrid film and the application of the laminate. From the viewpoint of crack resistance, the thickness of the above-mentioned organic-inorganic hybrid film may be typically 1 μm 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, from the viewpoint of reliably obtaining the properties and functions to be imparted by the above-mentioned organic-inorganic hybrid film, the thickness may be typically 1 nm or more, preferably 10 nm or more, more preferably 20 nm or more, even more preferably 30 nm or more, and most preferably 40 nm or more.

[0071] 5. First Embodiment: An example of an embodiment of the present invention for manufacturing an organic-inorganic hybrid film, using a roll-to-roll sputtering apparatus as conceptually shown in Figure 1, will be described.

[0072] First, inorganic targets 9 and 9' are mounted on target mounting fixtures 8 and 8', respectively. Inorganic targets 9 and 9' may be made of the same inorganic material, or they may be made of different inorganic materials. From the viewpoint of uniformity of the composition of the organic-inorganic hybrid film, inorganic targets 9 and 9' may preferably be made of the same inorganic material.

[0073] Next, the film substrate 10 is fed through. That is, the film roll 12 of the film substrate 10 is set on the dispensing roll 2, and the winding tube (not shown) is set on the winding roll 5. The film substrate 10 is then dispensed from the film roll 12, held by the sputtering roll 4 via the transfer roll 3, and then wound up by the winding tube set on the winding roll 5 via the transfer roll 3'. Note that the feeding of the film substrate 10 may be performed before the inorganic material targets 9 and 9' are attached to the target setting jigs 8 and 8', respectively.

[0074] Next, the sputtering chamber 1 is evacuated from the exhaust port 7 by an exhaust device, reducing the pressure inside the sputtering chamber 1 to below a predetermined pressure during film deposition. The predetermined pressure is usually 10 -5 ~10 -2 Approximately Pa, preferably 10 -4 ~6×10 -3 A Pa level is sufficient.

[0075] Next, a mixed gas of the sputtering gas and the organic compound gas is introduced into the sputtering chamber 1 from the sputtering gas inlet 6 so that the pressure inside the sputtering chamber 1 is predetermined during film formation. At this time, the sputtering gas and the organic compound gas may be prepared separately and introduced while combining and mixing the gas flows of both, or the mixed gas of the sputtering gas and the organic compound may be prepared in advance and introduced. Alternatively, the amount of the mixed gas introduced may be kept fixed, and the opening of the exhaust port 7 may be feedback controlled to keep the sputtering pressure constant.

[0076] The mixing ratio of the sputtering gas and the organic compound gas can be appropriately determined from the viewpoint of ensuring 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, and from the viewpoint of sputtering efficiency. The mixing ratio of the sputtering gas and the organic compound gas (volume of sputtering gas / volume of organic compound gas) depends on the type of organic compound, but is usually 60 / 40 to 99.999 / 0.001, preferably 70 / 30 to 99.99 / 0.01, more preferably 80 / 20 to 99.95 / 0.05, and even more preferably 90 / 10 to 99.9 / 0.1.

[0077] The sputtering gas mentioned above is not particularly limited as long as it is a gas that can be used for sputtering, and may be any known sputtering gas. Examples of the sputtering gas include inert gases such as argon and krypton, as well as mixed gases of these with oxygen and nitrogen.

[0078] When using an organic compound that turns into a gas upon heating (usually below the upper limit temperature at which the film substrate can be used) and / or reduced pressure, it goes without saying that it should be brought to a predetermined temperature and pressure before use to be in a gaseous state. In this case, it is preferable that the temperature inside the sputtering chamber 1 also be set to a predetermined temperature.

[0079] The predetermined pressure (sputtering pressure) inside the sputtering chamber 1 during the above-mentioned film deposition is usually 0.05 to 5 Pa, preferably 0.1 to 1 Pa, from the viewpoint of stabilizing the discharge and enabling continuous film deposition.

[0080] Next, predetermined power (usually high-frequency power) is applied to the inorganic targets 9 and 9' to cause discharge, and once the discharge state stabilizes, the film substrate 10 is moved at a predetermined line speed to form an organic-inorganic hybrid film on the surface of the film substrate 10. At this time, cooling water at a predetermined flow rate and temperature is flowed through the target installation jigs 8 and 8' to control the temperature of the inorganic targets 9 and 9' to a predetermined temperature.

[0081] While not intending to be bound by theory, the reason why the sputtered film formed is an organic-inorganic hybrid film, even though only the inorganic target is directly subjected to power, is that the gas of organic compounds present near the inorganic target is captured by the magnetic field generated when power is applied to the inorganic target, and is repelled upon by collisions with the sputtered gas and plasma-like sputtered gas present at high density within that magnetic field. In other words, by applying power to the inorganic target and sputtering, the gas of organic compounds is also sputtered along with it.

[0082] The composition of the above 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) can be adjusted to the desired composition by controlling the power supplied to the inorganic targets 9 and 9', and the mixing ratio of the sputtering gas and the organic compound gas. The relationship between the power supplied, the mixing ratio, and the composition can be determined by conducting preliminary experiments.

[0083] The thickness of the above organic-inorganic hybrid film can be adjusted to the desired thickness by controlling the power supplied to the inorganic targets 9 and 9', the mixing ratio of the sputtering gas and the organic compound gas, the flow rate of the mixed gas (pressure in the sputtering chamber 1 during film formation), and the line speed (travel speed of the film substrate 10). The relationship between the power supplied, the mixing ratio, the flow rate of the mixed gas, the line speed, and the film thickness can be determined by conducting preliminary experiments. The film substrate 10 may also be moved back and forth over a predetermined distance, passing over the position of the sputtering roll 4 facing the inorganic targets 9 and 9' (i.e., the position where the organic-inorganic hybrid film is formed) two or more times. Increasing the line speed (travel speed of the film substrate 10) can suppress problems such as the film substrate 10 bending due to heat or the organic-inorganic hybrid film cracking due to the bending of the film substrate 10. Furthermore, it becomes easier to ensure a stable line speed even when trying to increase the thickness of the organic-inorganic hybrid film.

[0084] The thickness of the organic-inorganic hybrid film can be appropriately determined considering the function to be imparted to the organic-inorganic hybrid film and the intended use of the laminate or molded article having the organic-inorganic hybrid film on at least one surface of the substrate.

[0085] When attempting to impart a low ultraviolet transmittance to the above-mentioned organic-inorganic hybrid film, the film thickness of the organic-inorganic hybrid film may be typically 1 nm or more, preferably 10 nm or more, more preferably 20 nm or more, even more preferably 30 nm or more, and most preferably 40 nm or more, from the viewpoint of lowering ultraviolet transmittance. On the other hand, from the viewpoint of crack resistance, the film thickness may be typically 1 μm 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.

[0086] After forming the above organic-inorganic hybrid film, it is preferable to perform an annealing treatment at a temperature of 50°C or higher, preferably 80°C or higher, more preferably 100°C or higher, and below a temperature that takes into account the heat resistance of the film substrate 10, and preferably at a temperature of 150°C or lower from the viewpoint of workability and productivity. This can stabilize the properties of the above organic-inorganic hybrid film.

[0087] 6. Second Embodiment: An example of an embodiment of the present invention for manufacturing an organic-inorganic hybrid film, using a batch-type sputtering apparatus as shown in the conceptual diagram in Figure 3, is described below.

[0088] First, inorganic targets 16 and 16' are mounted on target mounting fixtures 15 and 15', respectively. Inorganic targets 16 and 16' may be made of the same inorganic material, or they may be made of different inorganic materials. From the viewpoint of uniformity of the composition of the organic-inorganic hybrid film, inorganic targets 16 and 16' may preferably be made of the same inorganic material.

[0089] Next, the substrate 19 is attached to the sputtering table 18 and rotated at a predetermined rotational speed. The predetermined rotational speed of the sputtering table 18 is usually 1 to 1000 revolutions per minute, preferably 2 to 50 revolutions per minute. During the deposition of the organic-inorganic hybrid film, the rotational speed may remain constant, or it may be changed as desired.

[0090] Next, the sputtering chamber 20 is evacuated from the exhaust port 21 by an exhaust device to reduce the pressure inside the sputtering chamber 20 to below a predetermined pressure during film deposition. The predetermined pressure is usually 10 -5 ~10 -2 Approximately Pa, preferably 10 -4 ~5×10 -3 A Pa level is sufficient.

[0091] Next, a mixed gas of the sputtering gas and the organic compound gas is introduced into the sputtering chamber 20 from the sputtering gas inlet 22 so that the pressure inside the sputtering chamber 20 is predetermined during film formation. At this time, the sputtering gas and the organic compound gas may be prepared separately and introduced while combining and mixing the gas flows of both, or the mixed gas of the sputtering gas and the organic compound may be prepared in advance and introduced. Alternatively, the amount of the mixed gas introduced may be kept fixed, and the opening of the exhaust port 21 may be feedback controlled to keep the sputtering pressure constant.

[0092] The mixing ratio of the sputtering gas and the organic compound gas can be appropriately determined from the viewpoint of ensuring 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, and from the viewpoint of sputtering efficiency. The mixing ratio of the sputtering gas and the organic compound gas (volume of sputtering gas / volume of organic compound gas) depends on the type of organic compound, but is usually 60 / 40 to 99.999 / 0.1, preferably 70 / 30 to 99.99 / 0.01, more preferably 80 / 20 to 99.95 / 0.05, and even more preferably 90 / 10 to 99.9 / 0.1.

[0093] The sputtering gas mentioned above is not particularly limited as long as it is a gas that can be used for sputtering, and may be any known sputtering gas. Examples of the sputtering gas include inert gases such as argon and krypton, as well as mixed gases of these with oxygen and nitrogen.

[0094] When using an organic compound that turns into a gas upon heating (usually below the upper limit temperature at which the substrate can be used) and / or reduced pressure, it goes without saying that it should be brought to a predetermined temperature and pressure before use to be in a gaseous state. In this case, it is preferable that the temperature inside the sputtering chamber 20 also be set to a predetermined temperature.

[0095] The predetermined pressure (sputtering pressure) inside the sputtering chamber 12 during the above-mentioned film deposition is usually 0.05 to 5 Pa, preferably 0.1 to 1 Pa, from the viewpoint of stabilizing the discharge and enabling continuous film deposition.

[0096] Next, predetermined power (usually high-frequency power) is applied to the inorganic targets 16 and 16' to cause a discharge. Once the discharge state stabilizes, the shutters 17 and 17' are opened, and each target is sputtered to form an organic-inorganic hybrid film on the surface of the substrate 19. At this time, cooling water at a predetermined flow rate and temperature is flowed through the target setting jigs 15 and 15' to control the temperature of the inorganic targets 16 and 16' to a predetermined temperature. Furthermore, by keeping the shutters 17 and 17' closed until the discharge state stabilizes, it is possible to prevent contaminants such as dirt and water from adhering to the surface of the substrate 19 during pre-sputtering (an operation to remove contaminants such as dirt and water from the surface of the targets 16 and 16' (by blowing them off by applying power)).

[0097] The composition of the above 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) can be adjusted to the desired composition by controlling the power supplied to the inorganic targets 16 and 16', the mixing ratio of the sputtering gas and the organic compound gas, and the flow rate of the mixed gas (pressure in the sputtering chamber 20 during film formation). The relationship between the power supplied, the mixing ratio, the flow rate of the mixed gas, and the composition can be determined by conducting preliminary experiments.

[0098] The thickness of the above organic-inorganic hybrid film can be adjusted to the desired thickness by controlling the power supplied to the inorganic targets 16 and 16', the mixing ratio of the sputtering gas and the organic compound gas, the flow rate of the mixed gas (pressure in the sputtering chamber 20 during film formation), and the film formation time. The relationship between the power supplied, the mixing ratio, the flow rate of the mixed gas, and the film formation time can be determined by conducting preliminary experiments.

[0099] The thickness of the organic-inorganic hybrid film can be appropriately determined considering the function to be imparted to the organic-inorganic hybrid film and the intended use of the laminate or molded article having the organic-inorganic hybrid film on at least one surface of the substrate.

[0100] When attempting to impart a low ultraviolet transmittance to the above-mentioned organic-inorganic hybrid film, the film thickness of the organic-inorganic hybrid film may be typically 1 nm or more, preferably 10 nm or more, more preferably 20 nm or more, even more preferably 30 nm or more, and most preferably 40 nm or more, from the viewpoint of lowering ultraviolet transmittance. On the other hand, from the viewpoint of crack resistance, the film thickness may be typically 1 μm 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.

[0101] After forming the above organic-inorganic hybrid film, it is preferable to perform annealing at a temperature of 50°C or higher, preferably 80°C or higher, more preferably 100°C or higher, and below a temperature that takes into account the heat resistance of the substrate 19, and preferably at a temperature of 150°C or lower from the viewpoint of workability and productivity. This can stabilize the properties of the above organic-inorganic hybrid film.

[0102] In organic-inorganic hybrid films, the types of compounds formed by the inorganic substances and organic compounds used as raw materials can be confirmed by X-ray photoelectron spectroscopy (hereinafter sometimes abbreviated as "XPS analysis"). XPS analysis can be performed, for example, using an XPS analyzer and using aluminum Kα rays or magnesium Kα rays as the X-rays. For more information on XPS analysis, please refer to the following references. References: MPSeah and WADerch, Surface and Interface Analysis 1,2 (1979) [Examples]

[0103] The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0104] Measurement method (i) Sputter film thickness: The sputtered film thickness was determined by preliminary experiments. First, a heat-resistant, low-outgassing adhesive tape (Kapton Tape P-221, manufactured by Nitto Denko Corporation) was partially applied to the substrate beforehand. After sputtering, it was peeled off to create a step equal to the film thickness. Using a small surface roughness measuring instrument "SJ-411" manufactured by Mitutoyo Corporation, the shape profile of the step was measured at a measurement speed of 0.5 mm / s and a measurement distance of 1.5 mm, and the step read from this was defined as the sputtered film thickness.

[0105] (b) Analysis of sputtered films by X-ray photoelectron spectroscopy (XPS analysis) Using an XPS analyzer (Thermo Fisher Scientific K.K.'s "K-Alpha" (product name)), a wide-scan spectrum was measured using monochromatic aluminum Kα rays as X-rays, with an irradiation diameter of 400 μm, an electron extraction angle of 90 degrees, a pass energy of 200 eV, a measurement range of -10 to 1350 eV, an energy step of 1,000 eV, a step time of 10 ms, and 10 measurements. In addition, a narrow-scan spectrum of the F1s orbital (F1s) was measured for the energy region attributed to the fluorine atom 1s orbital (F1s) under the following conditions: electron extraction angle of 90 degrees, pass energy of 50 eV, measurement range of 678 to 698 eV, an energy step of 0,100 eV, a step time of 50 ms, and 10 measurements.

[0106] Raw materials used (A) Target material that is solid under standard conditions (temperature 25°C, pressure 100kPa): (A-1) A disc-shaped target with a diameter of 76.2 mm and a thickness of 3 mm, obtained by sintering cerium dioxide from USTRON Corporation. Purity: 4N. (A-2) A rectangular target measuring 127mm in length, 380mm in width, and 3mm in thickness, obtained by sintering cerium dioxide from USTRON Corporation. Purity: 4N. (A-3) A disc-shaped target made of polydimethylsiloxane (a silicon resin that does not contain fluorine atoms), with a diameter of 76.2 mm and a thickness of 3 mm.

[0107] (B) Gases of organic compounds: (B-1) Tetrafluoromethane (grade with a purity of 99.999% or higher).

[0108] (C) Base material: (C-1) Smooth soda-lime glass plate from Matsunami Glass Industry Co., Ltd. (Product name: Micro slide glass, polished edge, thickness: 1.0 mm, dimensions: 40 x 40 mm). (C-2) Lumirror (product name), a 125 μm thick, double-sided, easily bondable, biaxially oriented polyethylene terephthalate resin film from Toray Industries, Inc.

[0109] Example 1 A batch sputtering apparatus was used, and an organic-inorganic hybrid film was formed on one surface of the above (C-1) using the above (A-1) and the above (B-1). First, the above (A-1) was mounted on the target installation jig of the sputtering apparatus. Next, the sputtering chamber of the sputtering apparatus was evacuated to a pressure of 3.0×10 -3 Pa. Next, the gas flow of argon gas (grade with purity of 99.999% or more) as a sputtering gas (volume flow rate 23.4 sccm) and the gas flow of the above (B-1) (volume flow rate 2.6 sccm) were merged and introduced into the sputtering chamber while being mixed, and the shutter opening degree of the exhaust pipe portion was adjusted so that the pressure in the sputtering chamber became 0.8 Pa. Subsequently, power was input under the condition of input power of 200 W to the above (A-1) (input power per unit area 4.4 W / cm 2 ), sputtering was performed, and a sputtered film was formed on one surface of the above (C-1). At this time, the film formation time was 30 minutes, and it was the film formation condition in which the thickness of the sputtered film was 165 nm. XPS analysis was performed on the above sputtered film. The analysis results are shown in FIGS. 4 and 5. In the F1s narrow scan spectrum of FIG. 4, a peak derived from the F-Ce bond appears at 685.7 eV, so it was found that fluorine atoms derived from tetrafluoromethane modified cerium dioxide to produce cerium trifluoride. Also, the atomic ratio (F / Ce) of fluorine to cerium calculated from the wide scan spectrum of FIG. 5 was 3.7. From these results, it was found that the above sputtered film is an organic-inorganic hybrid film, that is, an organic-inorganic hybrid film can be formed by the method of the present invention.

[0110] In this specification, the unit "sccm" of volume flow rate is the volume (unit: cc) of gas flowing per minute normalized under standard conditions (temperature 0°C, 1 atm).

[0111] Example 2 The sputtered film was formed in the same manner as in Example 1, except that a gas flow of argon gas (volume flow rate 20.8 sccm) as the sputtering gas and the gas flow of (B-1) described above (volume flow rate 5.2 sccm) were introduced into the sputtering chamber while being combined and mixed. The deposition time was 30 minutes, and the deposition conditions resulted in a sputtered film thickness of 200 nm. XPS analysis was performed on the sputtered film. The analysis results are shown in Figures 6 and 7. In the F1s narrow scan spectrum in Figure 6, a peak originating from the F-Ce bond appears at 685.0 eV, similar to Example 1, indicating that fluorine atoms originating from tetrafluoromethane modified cerium dioxide to produce cerium trifluoride. Furthermore, the atomic ratio of fluorine to cerium (F / Ce) calculated from the wide scan spectrum in Figure 7 was 7.4. These results confirm that the composition of the sputtered film (organic-inorganic hybrid film) can be adjusted by the mixing ratio of the sputtering gas and the organic compound gas.

[0112] Example 3 Using a roll-to-roll sputtering apparatus, as conceptually shown in Figure 1, an organic-inorganic hybrid film was formed on one surface of (C-2) using (A-2) and (B-1) above. (1) First, the above (C-2) was fed through the sputtering apparatus, and then the above (A-2) (target 9) was mounted on the target mounting jig 8. The target mounting jig 8' was not used. In other words, only one of the above (A-2) was used. (2) Next, the sputtering chamber 1 of the sputtering apparatus is subjected to a pressure of 5.0 × 10 -3 The pressure was reduced to Pa. (3) Next, a gas flow (volume flow rate of 190 sccm) of argon gas (grade with a purity of 99.999% or higher) as the sputtering gas and the gas flow (volume flow rate of 10 sccm) from (B-1) above were combined and mixed and introduced into the sputtering chamber 1, and the shutter opening of the exhaust port 7 was adjusted so that the pressure in the sputtering chamber 1 was 0.4 Pa. (4) Next, while winding up (C-2) at a line speed of 1.0 m / min, input power of 1500 W (power input per unit area of ​​3.1 W / cm²) is applied to (A-2) (target 9). 2 Power was applied under the conditions described above, and sputtering was performed to form a sputtered film on one side of (C-2). At the same time, (C-2) was moved back and forth over a predetermined distance so that it passed nine times at the position of the sputtering roll 4 opposite (A-2) (target 9). The above sputtered film was deposited under conditions that resulted in a thickness of 50 nm. XPS analysis was performed on the sputtered film. The analysis results are shown in Figures 8 and 9. In the F1s narrow scan spectrum in Figure 8, a peak originating from the F-Ce bond appears at 682.5 eV, indicating that fluorine atoms from tetrafluoromethane modified cerium dioxide to produce cerium trifluoride. Furthermore, the atomic ratio of fluorine to cerium (F / Ce) calculated from the wide scan spectrum in Figure 9 was 3.6. These results confirm the formation of an organic-inorganic hybrid film.

[0113] Example 4 A sputtered film was formed in the same manner as in Example 3, except that the flow rate of the argon gas flow described above was changed to a volumetric flow rate of 199 sccm, and the flow rate of the gas flow described in (B-1) was changed to 1 sccm. The deposition conditions resulted in a sputtered film thickness of 50 nm. XPS analysis was performed on the sputtered film. The analysis results are shown in Figures 10 and 11. In the F1s narrow scan spectrum in Figure 10, a peak originating from the F-Ce bond appears at 681.5 eV, indicating that fluorine atoms originating from tetrafluoromethane modified cerium dioxide to produce cerium trifluoride. Furthermore, the atomic ratio of fluorine to cerium (F / Ce) calculated from the wide scan spectrum in Figure 11 was 1.7. From these results, it was confirmed that an organic-inorganic hybrid film was formed.

[0114] Although the present invention has been described in detail, these are merely illustrative examples. Those skilled in the art will be able to make various modifications within the bounds of the essential features of the present invention. Those skilled in the art may, for example, adopt the following manufacturing method. In this case, it goes without saying that the present invention can be implemented by appropriately substituting "target of inorganic compound" with "target of organic compound" and "organic-inorganic hybrid film" with "composite film" in the specification. Such a manufacturing method would be useful, for example, when forming a composite film or modified film in which fluorine atoms are introduced into a silicon resin by using a silicon resin target as the target of the organic compound and an organofluorine compound gas as the gas of the organic compound. [1]. A method for manufacturing a composite film, Using a sputtering device, Using a target of the first organic compound and a gas of the second organic compound, (1) A step of mounting the target of the first organic compound onto the target setting jig of the sputtering apparatus; (2) A step of reducing the pressure inside the sputtering chamber of the sputtering apparatus to a predetermined pressure; (3) A step of introducing a mixture of sputtering gas and the gas of the second organic compound into the sputtering chamber of the sputtering apparatus so that the pressure inside the sputtering chamber is predetermined; and, (4) A step of forming the composite film on the surface of the substrate by applying power to the target of the first organic compound and sputtering it; The above manufacturing method, including the above. [2]. The manufacturing method described in item [1], wherein the sputtering apparatus is a roll-to-roll sputtering apparatus. [3]. The manufacturing method according to item [1] or [2], wherein the mixing ratio of the above mixed gas (volume of the above sputtered gas / volume of the above second organic compound gas) is 60 / 40 to 99.999 / 0.001. [4]. A method for producing the second organic compound described above, comprising a gas of one or more compounds selected from the group consisting of compounds having a structure in which one or more hydrogen atoms of a saturated hydrocarbon are replaced by fluorine atoms and are gaseous under standard conditions (temperature 25°C, pressure 100kPa), and compounds having a structure in which one or more hydrogen atoms of an unsaturated hydrocarbon are replaced by fluorine atoms and are gaseous under standard conditions (temperature 25°C, pressure 100kPa), according to any one of the claims [1] to [3]. [5]. A method for producing the above organic compound, wherein the target comprises a silicone resin, as described in any one of items [1] to [4].

[0115] Example 5 The sputtered film was formed in the same manner as in Example 1, except that (A-3) was used instead of (A-1). The deposition time was 30 minutes, and the deposition conditions resulted in a sputtered film thickness of 200 nm. The sputtered film was analyzed by specular reflection FT-IR, and the appearance of peaks originating from CF bonding confirmed that fluorine atoms originating from tetrafluoromethane modified the silicon resin, i.e., a composite film was formed. [Brief explanation of the drawing]

[0116] [Figure 1] This is a conceptual diagram showing an example of a roll-to-roll sputtering apparatus. [Figure 2] This is a photograph showing an example of a roll-to-roll sputtering apparatus equipped with an anti-adhesion plate. [Figure 3] This is a conceptual diagram showing an example of a batch-type sputtering apparatus. [Figure 4] This is the spectrum obtained by XPS analysis of the sputtered film (organic-inorganic hybrid film) of Example 1, for the energy region attributed to the fluorine atom's 1s orbital. [Figure 5] This is the 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. [Figure 6]This is the 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's 1s orbital. [Figure 7] This is the 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. [Figure 8] This is the 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's 1s orbital. [Figure 9] This is the 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. [Figure 10] This is the spectrum obtained by XPS analysis of the sputtered film (organic-inorganic hybrid film) of Example 4, for the energy region attributed to the fluorine atom's 1s orbital. [Figure 11] This is the 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. [Explanation of Symbols]

[0117] 1: Sputtering chamber 2: Feed Roll 3, 3': Transfer Roll 4: Spatter Roll 5: Reel roll 6: Spatter gas inlet 7: Exhaust vent 8, 8': Target setting jig 9, 9': Target 10: Film substrate 11: Laminate 12, 12': Film roll 13: Anti-adhesion plate 14: Mounting jig for protective plate 15, 15': Target setting jig 16, 16': Target 17, 17': Shutter 18: Spatter Table 19: Base material 20: Sputtering chamber 21: Exhaust vent 22: Spatter gas inlet

Claims

1. 1. A method for producing a composite membrane, comprising the steps of: Using a sputtering device, (A) A target of solid material under standard conditions (temperature 25°C, pressure 100 kPa) (B) using a gas of a substance capable of preparing a mixed gas with the sputtering gas; (1) a step of mounting the (A) target on a target mounting jig of the sputtering apparatus; (2) reducing the pressure inside the sputtering chamber of the sputtering apparatus to a predetermined pressure; (3) introducing a mixed gas of the sputtering gas and the gas (B) into a sputtering chamber of the sputtering apparatus so that the pressure in the sputtering chamber is a predetermined pressure; and (4) applying power to the target (A) and sputtering the target to form the composite film on the surface of the substrate; wherein the gas (B) comprises a gas of an organic compound; The mixing ratio of the mixed gas (volume of the sputtering gas / volume of the (B) gas) is 70 / 30 to 99.999 / 0.001; The above manufacturing method.

2. 2. The method according to claim 1, wherein the sputtering apparatus is a roll-to-roll type sputtering apparatus.

3. 2. The method according to claim 1, wherein a mixing ratio of the mixed gas (volume of the sputtering gas / volume of the (B) gas) is 80 / 20 to 99.999 / 0.

001.

4. A manufacturing method as described in claim 1, wherein in step (4), the power input to the (A) target is high-frequency power.

5. 2. The method according to claim 1, wherein the organic compound gas comprises one or more compounds selected from the group consisting of compounds having a structure in which one or more hydrogen atoms of a saturated hydrocarbon are substituted with a fluorine atom and which are gaseous at the standard state, and compounds having a structure in which one or more hydrogen atoms of an unsaturated hydrocarbon are substituted with a fluorine atom and which are gaseous at the standard state.

6. The manufacturing method described in claim 1, wherein a resin is used as the substrate.

7. The method according to any one of claims 1 to 6, wherein the target (A) is an inorganic target.

8. The method of claim 7, wherein the inorganic target comprises an inorganic material having a band gap of 2.6 to 3.7 eV.

9. The method of claim 7, wherein the inorganic target comprises cerium oxide.

10. The sputtering apparatus is a roll-to-roll sputtering apparatus; The organic compound gas includes one or more compounds selected from the group consisting of a compound having a structure in which one or more hydrogen atoms of a saturated hydrocarbon are replaced by a fluorine atom and which is a gas under standard conditions, and a compound having a structure in which one or more hydrogen atoms of an unsaturated hydrocarbon are replaced by a fluorine atom and which is a gas under standard conditions; The (A) target is an inorganic target; the inorganic material target comprises an inorganic material having a band gap of 2.6 to 3.7 eV; The inorganic target comprises cerium oxide; The substrate is a resin film or a resin sheet; The method according to claim 4.

11. The method according to any one of claims 1 to 6, wherein the target (A) is an organic compound target.

12. The method of claim 11 , wherein the organic compound target comprises a silicone resin.

13. The sputtering apparatus is a roll-to-roll sputtering apparatus; The organic compound gas includes one or more compounds selected from the group consisting of a compound having a structure in which one or more hydrogen atoms of a saturated hydrocarbon are replaced by a fluorine atom and which is a gas under standard conditions, and a compound having a structure in which one or more hydrogen atoms of an unsaturated hydrocarbon are replaced by a fluorine atom and which is a gas under standard conditions; The (A) target is an organic compound target; The method of claim 4 , wherein the organic compound target comprises a silicone resin.

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