Silicon oxide coating film, molded article, filled article, and method for filling oil / fat

Abstract

The purpose of the present invention is to provide: a silicon oxide coating film which, even when being in contact with an oil / fat or an oil / fat composition for a long period of time, maintains good oil repellency and / or oil release, or suppresses deterioration of oil repellency and / or oil release; and a molded article. Specifically, the present invention provides a silicon oxide coating film for use in applications where the coating film comes into contact with an oil / fat or an oil / fat composition. With respect to the surface of the silicon oxide coating film, a component (γh) based on a hydrogen bond and a dipole-dipole interaction at 20°C is 2.4 mJ / m2 or less and / or a surface free energy (γ) at 20C is 26 mJ / m2 or less.

Description

Silicon oxide coated film, molded product, filled product, and method for filling with oil and fat

[0001] This invention relates to silicon oxide coating films, molded articles, and filled articles filled with oil and fat compositions. In particular, this invention relates to silicon oxide coating films that exhibit good oil drainage even when in contact with oil or oil and fat compositions for a long period of time, molded articles coated with the same silicon oxide coating film, filled articles using the molded articles, and filling methods.

[0002] Conventionally, to improve the properties of various substrates, films have been formed on their surfaces. For example, in packaging materials, a vapor-deposited film is formed on the surface of a plastic molded product by plasma CVD to improve its gas barrier properties (see Patent Documents 1 and 2).

[0003] On the other hand, if containers and cooking utensils are easy to clean after use and allow for easy draining of contents, work efficiency improves and the environmental burden decreases. Therefore, water-repellent and oil-repellent properties are also required as characteristics of the substrate for containers and cooking utensils. For oil repellency, the use of a specific silicon oxide coating film has been proposed (see Patent Document 3). However, there was a problem in that prolonged contact with oils or oil compositions reduced oil repellency and resulted in poor oil drainage.

[0004] Japanese Patent Publication No. 2000-255579, Japanese Patent Publication No. 2003-53873, Japanese Patent Publication No. 2023-95740

[0005] The object of the present invention is to provide a silicon oxide coating film that maintains good oil repellency and / or oil drainage even after prolonged contact with oils and fats or oil compositions, or that suppresses deterioration of oil repellency and / or oil drainage. Furthermore, the invention aims to provide a molded product that maintains good oil repellency and / or oil drainage even after prolonged contact with oils and fats or oil compositions. Additionally, it aims to provide a product in which oils and fats or oil compositions are filled into a molded product that drains oil well when the oils and fats or oil compositions are removed from the molded product.

[0006] The inventors have conducted thorough research and found that the silicon oxide coating film applied to the container has hydrogen bonding and components based on dipole-dipole interactions (γ hBy adjusting the surface free energy (γ) and / or surface free energy (γ), it has been found that the deterioration of oil repellency and / or oil drainage performance can be suppressed, or a certain level of oil repellency and / or oil drainage performance can be maintained, even after prolonged contact with oils or oil compositions, thus completing the present invention.

[0007] In other words, one aspect of the present invention may relate to the following: [1] A silicon oxide coating film used in applications in contact with oils or oil compositions, wherein the surface of the silicon oxide coating film has components (γ) based on hydrogen bonding and dipole-dipole interaction at 20°C. h ) is 2.4 mJ / m 2 The following and / or the surface free energy (γ) at 20°C is 26 mJ / m 2 The silicon oxide coating film is as follows, where the components (γh) based on hydrogen bonding and dipole-dipole interaction and the surface free energy (γ) are based on the Owens-Wendt theory. [2] The silicon oxide coating film has a surface component (γh) based on hydrogen bonding and dipole-dipole interaction at 20°C. h ) is 2.0 mJ / m 2 The following and / or the surface free energy (γ) at 20°C is 25 mJ / m 2The silicon oxide coating film according to [1] above, which is as follows: [3] The silicon oxide coating film according to [1] or [2] above, wherein the silicon oxide coating film is a silicon oxide vapor-deposited film. [4] The silicon oxide coating film according to any one of [1] to [3] above, wherein the silicon oxide coating film is a film derived from hexamethyldisiloxane. [5] A molded article used in applications where the silicon oxide coating film comes into contact with oils or fats or oil compositions, wherein the surface of the silicon oxide coating film is covered with the silicon oxide coating film according to any one of [1] to [4] above. [6] The molded article according to [5] above, wherein the molded article is a container, pipe, or cooking utensil, molded from a material selected from resin, glass, metal, clay, and paper. [7] A filled article obtained by filling the molded article according to [5] or [6] above with oils or fats or oil compositions. [8] A method for producing a filled product, comprising the steps of: coating a molded product with a silicon oxide coating film described in any of [1] to [4]; and filling the coated molded product with edible oil or edible oil composition to obtain a filled product.

[0008] According to the present invention, it is possible to provide manufacturing equipment, transport piping, containers, tableware, etc., having a silicon oxide coating film that exhibits good oil repellency and / or oil drainage performance over a long period of time for oils and fats or oil compositions. Furthermore, it is expected that manufacturing equipment, transport piping, containers, etc., coated on the surface with the silicon oxide coating film will have good oil repellency and / or oil drainage for oils and fats or oil compositions, making it easy to remove oil stains and improving the cleanability against oil stains. In addition, it is expected that the containers of the present invention will allow the stored oils and fats or oil compositions to be used up to the very end, making it less likely for oils and fats to remain in the container, and improving the recyclability of the containers.

[0009] Hereinafter, the present invention will be described in detail with examples. In the embodiments of the present invention, A (numerical value) to B (numerical value) means A or more and B or less. Note that the preferred embodiments and more preferred embodiments exemplified below can be used in appropriate combinations with each other regardless of the expressions such as "preferred" and "more preferred". In addition, the description of the numerical range is for illustration, and ranges obtained by appropriately combining the upper and lower limits of each range and the numerical values of the examples can also be preferably used regardless of the expressions such as "preferred" and "more preferred". Furthermore, terms such as "containing" or "including" may be appropriately read as "consisting essentially of" or "consisting only of".

[0010] [Silicon Oxide Coating Film] The silicon oxide coating film of the present invention is a silicon oxide coating film that comes into contact with an oil or an oil composition, and a component (hereinafter, γ h which may also be denoted as such) based on hydrogen bonding and dipole-dipole interaction on the surface of the silicon oxide coating film at 20 °C is 2.4 mJ / m 2 or less, and / or the surface free energy (hereinafter, which may also be denoted as γ) at 20 °C is 26 mJ / m 2 or less (however, the component (γh) based on hydrogen bonding and dipole-dipole interaction and the surface free energy (γ) are based on the Owens-Wendt theoretical formula). Generally, if the surface free energy is below a certain level, the affinity with an oil or an oil composition is impaired, and it is considered that an oil repellent function is exhibited. For example, in a silicon oxide coating film, even when the surface free energy (γ) is 40 mJ / m 2 it has a sufficient oil repellent effect and oil release property. However, when the silicon oxide coating film comes into contact with an oil or an oil composition for a long time, it is considered that the molecules of the oil component adhere to the surface of the silicon oxide coating film due to polar functional groups (such as hydrogen bonding) of the oil component molecules, and the oil repellent function is impaired, resulting in poor oil release. Therefore, the "component (γ hBy having the value of ")」 or the value of "surface free energy (γ)" below a certain level, hydrogen bonding and the like between the surface of the silicon oxide coating film and the components of the oil and fat can be suppressed, deterioration of the oil repellency effect can be suppressed, and good oil repellency can be sustained.

[0011] (Components based on hydrogen bonding and dipole-dipole interaction) In the present invention, the component based on hydrogen bonding and dipole-dipole interaction (γ) on the surface of the silicon oxide coating film at 20 °C h ) is 2.4 mJ / m 2 or less, even when in long-term contact with an oil and fat or an oil and fat composition, it can be a silicon oxide coating film that maintains a good state of oil repellency and / or oil repellency or suppresses deterioration of oil repellency and / or oil repellency. Note that the component based on hydrogen bonding and dipole-dipole interaction (γ) h ) is measured using the contact angle and can be calculated based on Owens and Wendt (Owens-Wendt). The component based on hydrogen bonding and dipole-dipole interaction (γ) on the surface of the silicon oxide coating film at 20 °C h ) is preferably 2.3 mJ / m 2 or less, or 2.0 mJ / m 2 or less, more preferably 0.4 to 2.0 mJ / m 2 , or 0.7 to 1.8 mJ / m 2 , or 0.9 to 1.7 mJ / m 2 , or 0.1 to 1.6 mJ / m 2 is even more preferably. The component based on hydrogen bonding and dipole-dipole interaction (γ) on the surface of the silicon oxide coating film at 20 °C h ) may further be 0.2 mJ / m 2 or more, 0.5 mJ / m 2 or more, or 0.8 mJ / m 2 or more, and may also be 2.3 mJ / m 2 or less, 1.9 mJ / m 2 or less, 1.8 mJ / m 2 or less, 1.5 mJ / m 2 or less, 1.3 mJ / m 2 or less, or 1.0 mJ / m 2 or less.

[0012] (Surface Free Energy) In this invention, the surface free energy (γ) of the silicon oxide coating film at 20°C is 26 mJ / m 2 The following conditions result in oil repellency and improved oil drainage. The surface free energy is measured using the contact angle and can be calculated based on Owens and Wendt (Owens-Wendt). The surface free energy of the silicon oxide coating film at 20°C is 25.5 mJ / m². 2 The following or 25.0 mJ / m 2 The following, or 24.9 mJ / m 2 The following is preferable: 10 to 24.9 mJ / m 2 , or 15-24.9 mJ / m 2 , or 20-24.9 mJ / m 2 This is even more preferable. The surface free energy of the silicon oxide coating film at 20°C is further 5.0 mJ / m 2 Above, 12.0mJ / m 2 Above, or 16.0 mJ / m 2 It may be greater than or equal to 24.8 mJ / m 2 Below, 24.5mJ / m 2 Below, 24.0mJ / m 2 Below, 23.8mJ / m 2 The following, or 23.6 mJ / m 2 The following is also acceptable.

[0013] (Coating Film) The silicon oxide coating film of the present invention is a silicon oxide film applied to molded articles, etc., and its surface has specific hydrogen bond and component values ​​based on dipole-dipole interaction, and / or specific surface free energy. The silicon oxide coating film of the present invention only needs to have a silicon oxide coating film on the surface that comes into contact with oil or oil composition, and may be a single film or a film consisting of multiple layers or compositions, where the outermost layer surface is a silicon oxide coating film. These silicon oxide coating films can be, for example, those coated with a silica coating agent containing a valuable compound. Alternatively, a silicon oxide vapor-deposited film can be used, which is formed by plasma treatment by plasma CVD on the surface of a substrate such as a molded article held in a plasma treatment chamber in an atmosphere containing an organosilicon compound, an arbitrary oxidizing gas, and optionally a carrier gas.

[0014] In the case of the plasma CVD method, an organosilicon compound is used as a silicon source for forming a silicon oxide vapor deposition film. Examples of the organosilicon compound include organosilane compounds (such as hexamethyldisilane, vinyltrimethylsilane, methylsilane, dimethylsilane, tetramethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, methyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane, etc.), organosiloxane compounds (such as octamethylcyclotetrasiloxane, 1,1,3,3 - tetramethyldisiloxane, hexamethyldisiloxane, etc.), diethoxydimethylsilane, dimethyldimethoxysilane, etc. In addition to these materials, silazanes such as hexamethyldisilazane and aminosilanes can also be used. These organosilicon compounds can be used alone or in combination of two or more. Also, silane (SiH4) and silicon tetrachloride can be used in combination with the above-described organosilicon compounds. As the organic functional group of the organosilicon compound, an organosilicon compound having only a functional group selected from a methyl group, a methoxy group, an ethyl group, and an ethoxy group is preferable, an organosilicon compound having an ethoxy group and / or a methoxy group is more preferable, and an organosilicon compound having only an ethoxy group is further preferable. Also, an organosilicon compound having only a methyl group is further preferable. Tetraethoxysilane, tetramethoxysilane, hexamethyldisilazane, hexamethyldisiloxane, etc. are preferable, and only hexamethyldisiloxane or an organosilicon compound containing hexamethyldisiloxane is more preferable.

[0015] As the oxidizing gas, oxygen or NOx is used, and oxygen is preferable. As the carrier gas and the gas for discharge stabilization, noble gases such as argon and helium are used.

[0016] The ratio of the flow rate (volume) of the oxidizing gas to the total flow rate (volume) of the reaction gas is, for example, 0 to 95% by volume, preferably 1 to 65% by volume or 1 to 60% by volume, more preferably 2 to 40% by volume or 2 to 30% by volume, and even more preferably 5 to 10% by volume. The flow rate of the reaction gas depends on the coating area of ​​the molded product to be processed, but for example, when coating the inner surface of a plastic container with a capacity of 400 mL to 1.5 L, it is preferable to supply a flow rate of 3 to 2000 sccm per container, particularly 5 to 600 sccm. "Sccm" means the amount of gas (cc or ml) that flows in one minute at 0°C and 1 atmosphere.

[0017] The conditions for plasma treatment are not particularly limited, but for example, in order to maintain a vacuum level at which glow discharge occurs, the pressure during film deposition is preferably 1 to 200 Pa, and more preferably 3 to 100 Pa. In this state, a silicon oxide coating film (silicon oxide vapor deposition film) is formed by glow discharge by supplying microwaves (300 MHz to 300 GHz) or high-frequency waves (1 to 300 MHz). For example, the microwave output is preferably in the range of 10 to 1000 W, and more preferably 20 to 1000 W. The microwave frequency is preferably 500 MHz to 30 GHz, more preferably 1 to 10 GHz, and even more preferably 1 to 5 GHz. The high-frequency output is preferably 20 to 1500 W, and more preferably 30 to 1500 W. The high-frequency frequency is preferably 1 to 100 MHz, more preferably 1 to 30 MHz, and even more preferably 10 to 15 MHz.

[0018] The silicon dioxide coating film of the present invention can achieve oil repellency and / or oil drainage of oil compositions by covering the surface, so the film thickness is not considered to have any particular effect. The film thickness is not particularly limited, but is preferably 1 to 800 nm, more preferably 5 to 500 nm, even more preferably 8 to 400 nm, especially preferably 10 to 300 nm, and most preferably 10 to 150 nm.

[0019] (Oils and fats or oil and fat compositions) In the present invention, oils and fats are mainly composed of triglycerides, and may also be glycerides containing monoglycerides, diglycerides (glycerin monofatty acid esters), etc. In addition, in the present invention, oil and fat compositions are oils and fats blended with other oils and fats, or components other than oils and fats.

[0020] As for fats and oils, animal and vegetable fats and oils, fats and oils synthesized from glycerin and fatty acids and fractions thereof, transesterified oils, hydrogenated oils, etc., can be used individually or in combination. Examples of animal and vegetable fats and oils include soybean oil, rapeseed oil, high-oleic rapeseed oil, sunflower oil, high-oleic sunflower oil, olive oil, safflower oil, high-oleic safflower oil, corn oil, cottonseed oil, rice oil, sesame oil, perilla oil, linseed oil, peanut oil, grapeseed oil, beef tallow, milk fat, fish oil, coconut oil, palm oil, palm kernel oil, etc. Examples of fats and oils synthesized from glycerin and fatty acids include fats and oils containing linear saturated fatty acids having 6 to 12 carbon atoms, preferably 8 to 10 carbon atoms, such as medium-chain triglycerides (MCTs) having 8 to 10 carbon atoms. Examples of fractionated oils include palm olein, palm superolein, palm stearin, and palm mid-fraction. Examples of transesterified oils include transesterified oils of palm oil or fractionated palm oil with other liquid oils, or transesterified oils of MCT and vegetable oil. Examples of hydrogenated oils include hydrogenated oils of animal and vegetable oils, hydrogenated oils of fractionated animal and vegetable oils, and hydrogenated oils of transesterified oils.

[0021] In an oil and fat composition, the components other than oils and fats are not particularly limited, but raw materials commonly used in oil and fat compositions can be used. Specifically, for example, emulsifiers such as nonionic surfactants and ionic surfactants can be used. For food applications, it is preferable to use one or more food-grade emulsifiers such as monoglycerides, diglycerides, organic acid monoglycerides, polyglycerin fatty acid esters, polyglycerin condensed ricinoleic acid esters, sucrose fatty acid esters, polysorbates, propylene glycol fatty acid esters, sorbitan fatty acid esters, sorbitol fatty acid esters, and lecithin. Furthermore, the content of emulsifiers is not particularly limited, but the content in the oil and fat composition is preferably 0.01 to 80% by mass, more preferably 0.1 to 50% by mass, and even more preferably 0.1 to 10% by mass, or 0.5 to 5% by mass, or 0.5 to 3% by mass, when the oil and fat composition is considered to be 100% by mass.

[0022] Furthermore, raw materials such as ethanol, pH adjusters, seasonings, colorants, fragrances, antioxidants, sugars, and sugar alcohols can be used as ingredients. The amount of these ingredients can be any amount as long as it does not impair the effects of the present invention, but for example, they can be contained in an amount of 10% by mass or less in the oil and fat composition (100% by mass), preferably 0 to 3% by mass or more than 0% by mass and 3% by mass or more than 0% by mass and 1% by mass or.

[0023] The oil and fat content in the oil and fat composition is not particularly limited, but the oil and fat content is preferably 20% by mass or more, or 20 to 99.99% by mass, more preferably 48% by mass or more, or 50.0 to 99.9% by mass, and even more preferably 88% by mass or more, or 90.0 to 99.9% by mass, or 95.0 to 99.5% by mass, or 97.0 to 99.5% by mass, when the oil and fat composition is considered to be 100% by mass.

[0024] [Molded Article] The molded article of the present invention has its surface coated with the silicon oxide coating film described above, and the silicon oxide coating film comes into contact with oil or oil composition. In other words, the coated molded article of the present invention includes a molded article substrate and the silicon oxide coating film coated on the surface of the molded article substrate. The surface coating may be all or part of the inner and outer surfaces of the molded article, but from the perspective of the discharge of contents, it is preferable that the inner surface of the molded article is coated. The aforementioned surface refers to the outermost layer of the molded article. Furthermore, the silicon oxide coating film of the present invention may have other coatings between the coated molded article substrate and the coating layer according to the present invention.

[0025] The molded article (substrate) of the present invention is preferably molded from a material selected from the group consisting of resin, glass, metal, and paper. By having the aforementioned silicon oxide coating film on the surface of the molded article, a molded article can be obtained that is provided with oil stain prevention and improved oil removal. Suitable resins include thermoplastic resins that are known themselves, such as low-density polyethylene, high-density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, polyolefins (for example, polyolefins such as random or block copolymers of α-olefins such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene), ethylene-vinyl compound copolymers (for example, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl chloride copolymer, etc.), styrene-based resins (for example, polystyrene, acrylonitrile-styrene copolymer, A Examples of resins include biodegradable resins such as BS, α-methylstyrene / styrene copolymer, polyvinyl compounds (e.g., polyvinyl chloride, polyvinylidene chloride, vinyl chloride / vinylidene chloride copolymer, methyl polyacrylate, polymethyl methacrylate, etc.), polyamides (e.g., nylon 6, nylon 6-6, nylon 6-10, nylon 11, nylon 12, etc.), thermoplastic polyesters (e.g., polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polycarbonate, polyphenylene oxide, polylactic acid, or mixtures thereof. More preferably, the resin is polyethylene, polyethylene terephthalate, etc. As for the metal, one or more metals selected from iron, nickel, copper, zinc, lead, aluminum, chromium, titanium, etc., or alloys containing one or more of these metals as main components are preferred, and stainless steel is more preferred.

[0026] These molded products may be films, sheets, pipes, containers, etc., or they may be tableware, cooking utensils, and manufacturing equipment. Examples of pipes include tubes, valves, and nozzles. Examples of containers include bottles, tanks, cups, plastic wrap, bags, plates, etc., as well as caps, nozzles, etc., that make up the containers. Examples of tableware other than containers include chopsticks, spoons, forks, and knives. Examples of cooking utensils include strainers, meshes, stoves, microwave ovens, etc., as well as ventilation fans and countertops attached to kitchens. Examples of manufacturing equipment include food processing machinery, manufacturing equipment for components such as plastic injection molding machines and semiconductor component manufacturing equipment, and manufacturing equipment for chemicals and pharmaceuticals. In particular, it is preferable that the molded products be bottles, tanks, valves, nozzles, etc., for oils and fats. Furthermore, it is preferable that the oils and fats are edible. The portion of the molded product to be coated with the silicon oxide coating film may be all or part of the molded product, and in particular, it may be just the surface portion that comes into contact with the oil or oil composition.

[0027] [Filled Product] The filled product of the present invention is a molded product coated with the aforementioned silicon oxide coating film, filled with the aforementioned oil or oil composition. In other words, the filled product includes the coated molded product and the oil or oil composition filled into the molded product. An example of a filled product is a molded product (container) made of resin, glass, or metal coated with a silicon oxide coating film, filled with an oil composition for edible use.

[0028] [Method for Manufacturing Filled Products] The method for manufacturing the filled products of the present invention involves filling a molded product coated with the aforementioned silicon oxide coating film with the aforementioned edible oil or edible oil composition. More specifically, the above manufacturing method includes the steps of coating a molded product (substrate) with a silicon oxide coating film, and filling the coated molded product with edible oil or edible oil composition to obtain a filled product. For example, a molded product (container) made of resin, glass, or metal coated with a silicon oxide coating film is filled with edible oil or edible oil composition. This makes it possible to obtain a filled product that has good oil repellency and / or oil drainage over a long period of time.

[0029] Next, the present invention will be described in more detail with reference to examples, comparative examples, and reference examples, but the present invention is not limited in any way to these. Also, in the following, "%" refers to mass % unless otherwise specified.

[0030] [Comparative Examples 1-6, Examples 1-5] Multiple samples of the following samples 1-11 were prepared. The manufacturing conditions for samples 2-11 are described in the (Sample) column below. In addition, the "components based on hydrogen bonding and dipole-dipole interaction (γ)" of each sample were also described. h The following parameters were measured: "oil repellency," "surface free energy (γ)," and "oil contact angle." Oil repellency and / or oil drainage were evaluated by "oil slipperiness" and "reduction rate of residual oil amount." Samples 1-11 were filled with 600 g of refined rapeseed oil ("Nisshin Canola Oil," manufactured by Nisshin Oillio Group, Ltd.), capped, and sealed. The sealed containers containing the refined rapeseed oil were stored at a high temperature (dark place, 60°C, 8 weeks), and the "oil contact angle" was measured. Oil repellency and / or oil drainage were evaluated by "oil slipperiness" and "reduction rate of residual oil amount." Samples 1-2 and 4-11 were filled with 600 g of refined rapeseed oil ("Nisshin Canola Oil," manufactured by Nisshin Oillio Group, Ltd.), capped, and stored in light (1000 Lux, room temperature, 6 weeks). After that, the "oil contact angle" was measured. Furthermore, oil repellency and / or oil drainage were evaluated based on "oil and grease sliding properties" and "reduction in residual oil and grease volume." The measurement results are shown in Tables 2 and 3.

[0031] [Analysis] (Components and surface free energy based on hydrogen bonding and dipole-dipole interaction) A contact angle meter ("DMo-502", manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the surface free energy using the "Surface Free Energy Analysis [Component Calculation B]" setting on the contact angle meter. The liquids used for measuring the contact angle were pure water and diiodomethane (CAS RN: 75-11-6), with a liquid volume of 2.0 μL used for each measurement. The value was recorded 1 second after application. The temperature during measurement was room temperature (20°C). The θ / 2 method was used for the contact angle analysis (the radius r and height h of the droplet were determined by image processing, and θ was calculated as θ = 2arctan(h / r)). The surface free energy was determined from the contact angles of pure water and diiodomethane. The theoretical formula used to calculate the surface free energy (γ) was "Owens-Wendt". Note that the dispersion component (γ) of pure water was also used. d ) is 21.8 mJ / m 2 , components based on hydrogen bonding and dipole-dipole interactions (γ h ) is 51.0 mJ / m 2 The surface free energy (γ) is 72.8 mJ / m 2 The value of was used. Also, the dispersion component of diiodomethane (γ d ) is 49.5 mJ / m 2 , components based on hydrogen bonding and dipole-dipole interactions (γ h ) is 1.3 mJ / m 2 The surface free energy (γ) is 50.8 mJ / m 2 The value of was used. Note that the variance component (γ) in the table d ), components based on hydrogen bonding and dipole-dipole interactions (γ h The units of surface free energy (γ) are "mJ / m 2 "

[0032] (Contact angle of oil: In Tables 2-3, this is referred to as "contact angle") A contact angle meter ("DMo-502," manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the contact angle using the "Contact Angle Measurement [Droplet Method]" setting on the contact angle meter. The liquid used for measuring the contact angle was refined rapeseed oil ("Nisshin Canola Oil," manufactured by Nisshin Oillio Group Ltd.), and the amount of liquid used for each measurement was 2.0 μL. A "Teflon® coated needle" (manufactured by Kyowa Interface Science Co., Ltd.) was used to supply the oil to the contact angle meter. Since the oil has high viscosity and spreads over time after being applied to the silicon oxide vapor-deposited film sample of the examples and comparative examples, the value at 50 seconds after application, when the contact angle stabilizes to a certain extent, was recorded. The θ / 2 method was used for analysis (the radius r and height h of the droplet were determined by image processing, and θ was calculated as θ = 2arctan(h / r)).

[0033] (Slipperiness of oil: Indicated as "Slipperiness" in Tables 2-3) A 2 cm square PET plate was cut from the flat part of the container of samples 1-11, and one drop (approximately 24.36 mg) of colored oil (carotene: "β-Carotene 30% FS" manufactured by DMS Co., Ltd., 0.1% by mass; refined rapeseed oil: "Nisshin Canola Oil" manufactured by Nisshin Oillio Group Ltd., 99.9% by mass) was dropped onto it using a dropper. Immediately, the sample was placed on a stage set at a 70° inclination with respect to the vertical ("Stage (Angular Inclination)" manufactured by AS ONE Corporation), and the time it took for the trailing end of the oil droplet (the uppermost contact point between the sample surface and the oil droplet on the inclined surface of the sample to be evaluated) to move 6 mm across the sample surface was measured. The temperature during measurement was room temperature (23°C). Based on the movement time, evaluation was performed according to the following criteria A to E. A is the best rating, and E is the worst. Ratings A through D indicate good oil-repellent properties and / or oil-repellent effects. Furthermore, the shorter the travel time, the higher the oil-repellent properties and / or oil-repellent effects, indicating a better result. A: within 10 seconds; B: over 10 seconds to 20 seconds; C: over 20 seconds to 60 seconds; D: over 60 seconds to 300 seconds; E: over 300 seconds

[0034] (Reduction rate of residual oil) Samples 1 to 11 were filled with 600 g of refined rapeseed oil ("Nisshin Canola Oil," manufactured by Nisshin Oillio Group, Ltd.) in their respective containers. After removing the caps and opening the top of the containers, the containers were quickly tilted at an angle of 160° to the vertical to drain the refined rapeseed oil. For the stored samples, the caps that had been attached before storage were removed and the refined rapeseed oil was drained. The time when the refined rapeseed oil began to drain from the top of the container was defined as 0 seconds, and after 600 seconds, the containers were returned to their original position, and the amount of rapeseed oil remaining in the containers (residual oil) was measured. The tests were conducted at room temperature (23°C). When the residual oil amount of Sample 1 (Comparative Example 1) was set to B (mass%), and the residual oil amount of each example or comparative example of Samples 2 to 11 was set to A (mass%), the reduction rate of residual oil was calculated using the following formula. Percentage reduction in residual oil volume (%) = (1 - A / B) × 100

[0035] [Samples] (Samples 1-11) Sample 1 was an uncoated, commercially available polyethylene terephthalate container for edible oils and fats (PET container: usable capacity 600g, inner diameter of the opening at the top 30.3 mm, height 218.7 mm). Sample 1 was coated with a silicon oxide vapor-deposited film by plasma treatment using a plasma CVD apparatus (details below) with organosilicon compounds as raw materials under the film formation conditions shown in Table 1, and these were used as Samples 2-11 for Comparative Examples 2-6 and Examples 1-5. Specifically, tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), or hexamethyldisiloxane (HMDSO) were used as organosilicon compounds. Oxygen (O2) was mixed with the organosilicon compounds as an oxidizing gas as needed and used as a reaction gas. In addition, helium (He) was used as a carrier gas for TEOS and argon (Ar) was used as a discharge stabilizing gas as needed. First, the PET container was placed in the plasma processing chamber of the plasma CVD apparatus. After reducing the pressure in the plasma processing chamber to 1 Pa or less, the reaction gas and optionally argon gas were introduced into the plasma processing chamber at the flow rates shown in Table 1. The pressure was stabilized to the levels shown in Table 1 over 30 to 60 seconds. Then, a silicon oxide vapor deposition film was coated onto the surface of the PET container by discharging at the plasma output and time shown in Table 1. After the discharge, the introduction of the reaction gas, optional carrier gas, and discharge stabilizing gas was stopped, the pressure in the deposition chamber was reduced to 1 Pa or less, and the plasma processing chamber was opened to the atmosphere. The PET container was then removed from the plasma processing chamber and designated as samples 2 to 11.

[0036] <Plasma CVD Equipment> The conditions for film deposition using the plasma CVD equipment are as shown in Table 1. In addition, the settings for the plasma CVD equipment other than those shown in Table 1 are as follows: Name: Plasma CVD equipment Film deposition method: PECVD (Plasma Enhanced Chemical Vapor Deposition) Plasma source: CCP (Capacitively Coupled Plasma) Electrode shape: Similar type (relative to the container shape) External RF electrode: Upper and lower 2-piece structure, no cooling mechanism Internal gas introduction electrode: φ6.35mm, no heating mechanism Material: Aluminum alloy (external electrode), SUS304 (internal electrode) RF power supply: Frequency 13.56MHz RF switch: 2ch Matching method: Automatic impedance matching Exhaust configuration: Mechanical booster pump (main), rotary pump (auxiliary) Exhaust manifold External dimensions: 350mm x 350mm x H150mm

[0037]

[0038]

[0039]

[0040] As shown in Tables 2 and 3, all of the samples 2 to 11, which have a silicon oxide coating film, showed good results in terms of the reduction rate of residual oil and slipperiness before storage. However, the components of the silicon oxide coating film surface based on hydrogen bonding and dipole-dipole interaction at 20°C (γ h ) is 2.4 mJ / m 2 Below, the surface free energy (γ) at 20°C is 26 mJ / m 2 Samples 2-6 that do not meet any of the following criteria show a significant reduction in residual oil and a decrease in slipperiness. On the other hand, the components (γ) on the surface of the silicon oxide coating film are based on hydrogen bonding and dipole-dipole interactions at 20°C. h ) is 2.4 mJ / m 2 The following conditions apply, or the surface free energy (γ) at 20°C is 26 mJ / m 2 Samples 7-11, as described below, show a reduced rate of residual oil and a suppressed decrease in slipperiness.

[0041] The heating test was conducted at 60°C for 8 weeks and is generally considered an accelerated test of storage at room temperature (20°C). Since a 10°C increase in temperature approximately doubles the rate of chemical reactions, 8 weeks at 60°C is equivalent to 128 weeks (8 weeks x 16) of storage at room temperature (20°C). Therefore, it can be predicted that samples 2 to 11 will maintain their oil-repellent properties and / or oil-repellent properties for a long period of up to 128 weeks at room temperature.

Claims

1. A silicon oxide coating film used in applications involving contact with oils or oil compositions, wherein the surface of the silicon oxide coating film contains components based on hydrogen bonding and dipole-dipole interactions at 20°C (γ h ) is 2.4 mJ / m 2 The following and / or the surface free energy (γ) at 20°C is 26 mJ / m 2 The following is the case, where the component based on hydrogen bonding and dipole-dipole interaction (γ h The surface free energy (γ) of the silicon oxide coated film is based on the Owens-Wendt theoretical formula.

2. The component (γ) on the surface of the silicon oxide coating film based on hydrogen bonding and dipole-dipole interaction at 20°C h ) is 2.0 mJ / m 2 The following and / or the surface free energy (γ) at 20°C is 25 mJ / m 2 The silicon oxide coating film according to claim 1 is as follows:

3. The silicon oxide coating film according to claim 1 or 2, wherein the silicon oxide coating film is a silicon oxide vapor-deposited film.

4. The silicon dioxide coating film according to any one of claims 1 to 3, wherein the silicon dioxide coating film is a film derived from hexamethyldisiloxane.

5. A molded article whose surface is coated with a silicon oxide coating film according to any one of claims 1 to 4, for use in applications where the silicon oxide coating film comes into contact with oils or oil compositions.

6. The molded article according to claim 5, wherein the molded article is a container, pipe, or cooking utensil, formed from a material selected from resin, glass, metal, clay, and paper.

7. A filled product comprising a molded article according to claim 5 or 6 and an oil or oil composition filled into the molded article.

8. A method for producing a filled product, comprising the steps of: coating a molded product with a silicon oxide coating film according to any one of claims 1 to 4; and filling the coated molded product with edible oil or an edible oil composition to obtain a filled product.

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