TW202536230A - Silicon oxide vapor-deposited film, molded article containing the film, and method for producing the molded article - Google Patents

Abstract

The purpose of this invention is to provide a silicon oxide vapor deposition film with high slip properties and/or oleophobic properties of grease or grease-containing compositions, and a molded article of a silicon oxide vapor deposition film coating with high slip properties and/or oleophobic properties of grease. Specifically, a silicon oxide vapor deposition film is provided, wherein the ratio of ionic strength AO to ionic strength B (ionic strength AO/ionic strength B) in the ionic strength obtained by time-of-flight secondary ionic mass analysis on the surface of the silicon oxide vapor deposition film is 26 or more.

Description

Silicon oxide vapor-coated film and molded articles containing such film

This invention relates to a silicon oxide vapor deposition film and a molded article coated with the silicon oxide vapor deposition film. In particular, this invention relates to a silicon oxide vapor deposition film with high slip resistance and/or oleophobic properties for grease or grease-containing compositions and a molded article containing the film.

Previously, films were formed on surfaces to improve the properties of various substrates. For example, in packaging materials, vapor-deposited films are formed on the surface of molded plastic articles using the plasma chemical vapor deposition (CVD) method to improve gas barrier properties.

For example, a method for manufacturing a plastic container is known, characterized in that: when at least an organosilicon compound and oxygen or an oxidizing gas are used, and a barrier layer (vapor deposition film) is formed on at least one side of the plastic container using plasma CVD, namely, a barrier layer (vapor deposition film) containing silicon oxide and at least one of a compound containing at least one or more elements selected from carbon, hydrogen, silicon and oxygen, the concentration of the organosilicon compound changes. Furthermore, the gas flow ratio of the organosilicon compound (hexamethyldisiloxane) to oxygen is 1:2, 1:20, or 1:100 (see Patent Document 1).

In addition, it is shown that a silicon oxide film manufactured with a flow ratio of organosilicon compound gas to oxygen-containing gas in the range of 1:3 to 50, and containing a component ratio of 100 Si atoms, 170 to 200 O atoms, and 30 or less C atoms, has gas barrier properties (see Patent Document 2).

On the other hand, for items such as containers or cooking utensils, good cleanability and drainage after use improve workability and reduce environmental impact. Therefore, the properties of the substrate for containers or cooking utensils must be hydrophobic and oleophobic. Regarding hydrophobicity, for example, a bottle has been proposed in which an organic silicon compound film containing nitrogen, silicon, carbon, and hydrogen is formed, and a silicon oxide compound film with silicon oxide as the main component is formed on its surface using a CVD method (the gas flow ratio of hexamethyldisiloxane to oxygen is 1:4), thereby achieving good drainage (see Patent 3). Additionally, a molded article has been proposed that is coated with a silicon oxide vapor-deposited film with good oleophobic properties (Patent 4). However, the silicon oxide vapor-deposited film in Patent 4 has the following problem: although it is oleophobic, this oleophobicity deteriorates with prolonged contact with oils or contact with oils at high temperatures. Sufficient research has not been conducted on silicon oxide films that maintain good oleophobicity over long periods or at high temperatures. [Prior Art Documents] [Patent Documents]

[Patent Document 1] Japanese Patent Application Publication No. 2000-255579 [Patent Document 2] Japanese Patent Application Publication No. 2003-53873 [Patent Document 3] Japanese Patent Application Publication No. 2009-46162 [Patent Document 4] Japanese Patent Application Publication No. 2023-95740

The present invention addresses the problem of providing a silicon oxide vapor deposition film that retains the slip-off properties and/or oleophobic functions of oils or oil-containing compositions even when in contact with oils or oil-containing compositions for a long period of time or at high temperatures, and further provides a molded article of a silicon oxide vapor deposition film coating that retains the slip-off properties and/or oleophobic functions of oils or oil-containing compositions even when in contact with oils or oil-containing compositions for a long period of time or at high temperatures.

Through diligent research, the inventors discovered that by using a silicon oxide vapor deposition film containing hydroxyl and alkoxy groups in a certain proportion, a coating film and a molded article having the coating film can be obtained that exhibits high slip resistance and/or oleophobic function to oils or oil-containing components even when in contact with oils or oil-containing components for a long time or at high temperatures, thus completing the present invention.

That is, one aspect of the present invention may be the content related to the following. [1] A silicon oxide vapor deposition film, wherein of the ionic strengths obtained by time-of-flight secondary ionic mass analysis on the surface of the silicon oxide vapor deposition film, the ratio of ionic strength AO to ionic strength B (ionic strength AO/ionic strength B) is 26 or more. (Wherein, ionic strength B is the sum of the strengths of all ions with m/z of 78.99 and m/z of 138.95; ionic strength AO is the sum of the strengths of all ions with m/z of 31.02, m/z of 59.00, m/z of 74.99, m/z of 102.97, and m/z of 134.96.) [2] The silicon oxide vapor deposition film as described in [1], wherein the ratio of ionic intensity R to ionic intensity A (ionic intensity R/ionic intensity A) in the ionic intensity obtained by time-of-flight secondary ionic mass analysis on the surface of the silicon oxide vapor deposition film is 0.3 or less. (Where, ionic strength A is the sum of the strengths of the positive ions with m/z of 43.00, m/z of 59.03, and m/z of 73.05, and ionic strength R is the sum of the strengths of the positive ions with m/z of 29.04 and m/z of 55.06) [3] The silicon oxide vapor deposition film as described in [1] or [2], wherein In the ionic strength measurements obtained using time-of-flight secondary ionic mass analysis on the surface of the silicon oxide vapor-deposited film, the ratio of ionic strength AO to ionic strength A (ionic strength AO/ionic strength A) is 0.1 or more, and/or the ratio of the sum of ionic strength A and ionic strength AO to ionic strength S ((ionic strength A + ionic strength AO)/ionic strength S) is 100 or more, and/or the ratio of ionic strength AO to ionic strength S (ionic strength AO/ionic strength S) is 30 or more. (Where, ionic strength S is the strength of a positive ion with m/z of 43.97, ionic strength A is the sum of the strengths of the positive ions with m/z of 43.00, m/z of 59.03, and m/z of 73.05) [4] A silicon dioxide vapor deposition film as described in any of [1] to [3], wherein the silicon dioxide vapor deposition film exhibits a slip resistance of less than 300 seconds in the following oil slip resistance test when rapeseed oil is used as the oil. Oil slippage: The time (in seconds) for the trailing end of an oil droplet of 24 ± 0.5 mg of rapeseed oil to travel 6 mm across the surface of a silicon oxide vapor-coated sample at 23 ± 3 °C, at a 70° angle relative to the lead. [5] A silicon oxide vapor-coated film as described in any of [1] to [4], wherein the silicon oxide vapor-coated film is derived from hexamethyldisiloxane. [6] A molded article whose surface is covered with a silicon oxide vapor-coated film as described in any of [1] to [5]. [7] A molded article as described in [6], wherein the molded article is a container, piping, or cooking utensil formed from a material selected from resin, glass, metal, clay, and paper. [8] A method of manufacturing a molded article, said molded article being coated with the silicon oxide vapor deposition film, said method comprising: (A) a step of preparing the molded article, and (B) a step of coating the surface of said molded article with the silicon oxide vapor deposition film as described in any one of [1] to [5]. [9] A method of manufacturing as described in [8], wherein said coating is performed by plasma CVD using an organosilicon compound and any oxidizing gas as the reaction gas. [10] A method of manufacturing as described in [8] or [9], wherein said silicon oxide vapor deposition film is a film derived from hexamethyldisiloxane.

This invention provides a silicon oxide vapor deposition film that exhibits excellent slip resistance and/or oleophobicity even after prolonged contact with greases or grease-containing components, or at high temperatures. In prolonged contact with greases, for example, it can maintain its function for more than 8 weeks at temperatures below 100°C or below 60°C, or for 128 weeks at temperatures below 40°C or near room temperature (23°C ± 3°C). Furthermore, in terms of heat resistance (high-temperature durability), it can maintain its function at temperatures between 100°C and 250°C, or between 150°C and 200°C. Additionally, molded articles with this silicon oxide vapor deposition film on their surface are expected to exhibit easy removal of grease contaminants and excellent cleanability of grease. In addition, when the molded product is a container, piping, etc., it can be expected to have good degreasing properties and be difficult to produce grease residue.

The present invention will now be described in detail with examples. Furthermore, in the embodiments of the present invention, A (numerical value) to B (numerical value) refers to A and below B. Furthermore, regarding the preferred or even better embodiments illustrated below, regardless of the use of terms such as "preferential" or "more preferred," they can be appropriately combined with each other. Additionally, the description of numerical ranges is illustrative; regardless of the use of terms such as "preferential" or "more preferred," the range obtained by appropriately combining the upper and lower limits of each range with the numerical values of the embodiments can be used. Moreover, terms such as "containing" or "including" can be appropriately changed to "substantially formed by" or "formed solely by."

[Silicon Oxide Evaporation Film] The silicon oxide evaporation film of the present invention is a silicon oxide evaporation film on the surface of which, in the ionic strength obtained by time-of-flight secondary ionic mass analysis, (a) the ratio of ionic strength AO to ionic strength B (ionic strength AO/ionic strength B) is 26 or more. The silicon oxide vapor deposition film of the present invention preferably has the following properties in the ionic strength obtained by time-of-flight secondary ionic mass analysis on the surface of the silicon oxide vapor deposition film: (b) the ratio of ionic strength R to ionic strength A (ionic strength R/ionic strength A) is 0.3 or less, and/or (c) the ratio of ionic strength AO to ionic strength A (ionic strength AO/ionic strength A) A silicon oxide vapor deposition film having an ion strength of 0.1 or higher, or 0.2 or higher, and/or (d) the ratio of the sum of ionic strength A and ionic strength AO to ionic strength S ((ionic strength A + ionic strength AO) / ionic strength S) is 100 or higher, and/or (e) the ratio of ionic strength AO to ionic strength S (ionic strength AO / ionic strength S) is 30 or higher. Wherein, ions s, ion a, ion ao, ion b, ion r, ionic strength S, ionic strength A, ionic strength AO, ionic strength B, and ionic strength R are as described below.

Ion s is a positive ion with an m/z of 43.97. Ion a is a positive ion with an m/z of 43.00, an m/z of 59.03, and an m/z of 73.05. Ion ao is a negative ion with an m/z of 31.02, an m/z of 59.00, an m/z of 74.99, an m/z of 102.97, and an m/z of 134.96. Ion b is a positive ion with an m/z of 78.99 and an m/z of 138.95. The ions r are positive ions with m/z of 29.04 and positive ions with m/z of 55.06.

Ionic strength S is the strength of a positive ion with m/z 43.97. Ionic strength A is the sum of the strengths of the positive ions with m/z 43.00, m/z 59.03, and m/z 73.05. Ionic strength AO is the sum of the strengths of the negative ions with m/z 31.02, m/z 59.00, m/z 74.99, m/z 102.97, and m/z 134.96. Ionic strength B is the sum of the strengths of the positive ions with m/z 78.99 and m/z 138.95. Ionic strength R is the sum of the strengths of the positive ions with m/z 29.04 and m/z 55.06.

Furthermore, in this invention, the ions detected by time-of-flight secondary ion mass analysis are identified by m/z (the value obtained by dividing the mass m of the ion by the valence of the ion: a value without dimensions). Additionally, the ion intensity (ionic strength) is a value dependent on the number of ions detected using time-of-flight secondary ion mass analysis (the value detected for each ion at each m/z).

The silicon oxide vapor deposition film of this invention can be manufactured by plasma CVD using a reactive gas containing organosilicon compounds. It is envisioned that by leaving hydroxyl groups and alkoxy groups in a certain proportion in the silicon oxide vapor deposition film, the film will exhibit the slipperiness and/or oleophobicity of grease or grease-containing components.

The content of hydroxyl and/or alkoxy and/or alkyl components in the silicon oxide vapor deposition film is related to the intensity of the peaks originating from functional groups obtained by analyzing the surface of the silicon oxide vapor deposition film using Time-of-Flight-Secondary Ion Mass Spectrometry (TOF-SIMS). Therefore, in the silicon oxide vapor deposition film of the present invention, a certain ratio between the ionic intensity of ions desiccated to contain hydroxyl and/or alkoxy and/or alkyl components in the time-of-flight-secondary ion mass spectrometry and the ionic intensity of ions desiccated to originate solely from silicon oxide is a necessary condition.

Furthermore, we can define an ion derived solely from silicon oxide (ion s) as a positive ion with an m/z of 43.97 (SiO), and its ionic strength is denoted as ionic strength S. Additionally, we can define alkyl-containing ions (ion a) as positive ions with an m/z of 43.00 ( _SiCH3 ), m/z of 59.03 ( _{SiC2H7 )} , and m/z of 73.05 ( _{SiC3H9 )} , and sum their ionic strengths to obtain ionic strength A. Furthermore, imagine that the ions containing alkoxy groups (ions ao) are negative ions with m/z of 31.02 (CH ₃ O), negative ions with m/z of 59.00 (SiCH ₃ O), negative ions with m/z of 74.99 (SiCH ₃ O ₂ ), positive ions with m/z of 102.97 (Si ₂ CH ₃ O ₂ ), and negative ions with m/z of 134.96 (Si ₂ CH ₃ O ₄ ). The sum of these ionic strengths is the ionic strength AO. Furthermore, the ions containing hydroxyl groups (ion b) are assumed to be positive ions with m _/ z of 78.99 ( _{SiO3H3 )} and m/z of 138.95 ( _{Si2O5H3 )} . The sum of these ionic strengths is the ionic strength B. Additionally, the _ions of only hydrocarbon ions (ion r) are assumed to be positive ions with m/z of 29.04 ( _{C2H5 )} and m/z of 55.06 ( _C4H7 ). The sum of these ionic strengths is the ionic strength R.

The silicon oxide vapor deposition film of the present invention is a silicon oxide vapor deposition film on the surface of which, in the ionic strength obtained by time-of-flight secondary ionic mass analysis, (a) the ratio of ionic strength AO to ionic strength B (ionic strength AO/ionic strength B) is 26 or more, preferably 30 or more, more preferably 50 or more, even more preferably 100 or more, even more preferably 150 or more, and particularly preferably 200 or more. The silicon oxide vapor deposition film of the present invention preferably has the following characteristics: (b) the ratio of ionic intensity R to ionic intensity A (ionic intensity R/ionic intensity A) on the surface of the silicon oxide vapor deposition film obtained by time-of-flight secondary ionic mass analysis is 0.3 or less, preferably 0.2 or less, and more preferably less than 0.1. (c) the ratio of ionic intensity AO to ionic intensity A (ionic intensity AO/ionic intensity A) is 0.1 or more, preferably 0.1 to 1.0, and more preferably 0.1 to 0.6. Alternatively, the silicon oxide vapor deposition film of the present invention is a silicon oxide vapor deposition film on the surface of which, in the ionic strength obtained by time-of-flight secondary ionic mass analysis, (d) the ratio of the sum of ionic strength A and ionic strength AO to ionic strength S ((ionic strength A + ionic strength AO) / ionic strength S) is 100 or more, preferably 200 or more, more preferably 300 or more, and even more preferably 400 or more. Furthermore, the silicon oxide vapor deposition film of the present invention is a silicon oxide vapor deposition film on the surface of the silicon oxide vapor deposition film, wherein the ratio of ionic strength AO to ionic strength B (ionic strength AO/ionic strength B) obtained by time-of-flight secondary ionic mass analysis is preferably 20,000 or less, or 16,000 or less, more preferably 15,000 or less, 13,500 or less, 800 or less, 500 or less, or 400 or less. Furthermore, in the silicon oxide vapor deposition film of the present invention, in the ionic strength obtained by time-of-flight secondary ionic mass analysis on the surface of the silicon oxide vapor deposition film, (b)' the ratio of ionic strength R to ionic strength A (ionic strength R/ionic strength A) can be 0.0 or more or greater than 0.0. Additionally, in the silicon oxide vapor deposition film of the present invention, in the ionic strength obtained by time-of-flight secondary ionic mass analysis on the surface of the silicon oxide vapor deposition film, (c)' the ratio of ionic strength AO to ionic strength A (ionic strength AO/ionic strength A) is preferably 1 or less, more preferably 0.6 or less. Furthermore, the silicon oxide vapor deposition film of the present invention is a silicon oxide vapor deposition film on the surface of which, in the ionic strength obtained by time-of-flight secondary ionic mass analysis, the ratio of (d)' ionic strength A and ionic strength AO to ionic strength S ((ionic strength A + ionic strength AO) / ionic strength S) is preferably 60,000 or less, or 45,000 or less, more preferably 42,000 or less, or 600 or less, and even more preferably 41,500 or less, or 500 or less.

In addition, as another example, the silicon oxide vapor deposition film of the present invention is a silicon oxide vapor deposition film on the surface of which, in the ionic strength obtained by time-of-flight secondary ionic mass analysis, (e) the ratio of ionic strength AO to ionic strength S (ionic strength AO/ionic strength S) can be 30 or more, preferably 40 or more, more preferably 80 or more, even more preferably 100 to 8000, and particularly preferably 100 to 5000.

Furthermore, regarding the ionic strengths, (f) the ratio of ionic strength A to ionic strength S (ionic strength A/ionic strength S) is preferably 80 or more, more preferably 200 or more, further preferably 300 or more, and particularly preferably 1000 or more. Here, regarding conditions (a) to (f) and (a)' to (d)', if condition (a) is satisfied, then one or more combinations of conditions (b) to (f) and (a)' to (d)' may also be satisfied or not satisfied.

Furthermore, in this invention, the time-of-flight secondary ion mass analyzer can be measured using commercially available devices, such as the time-of-flight secondary ion mass analyzer sold by Hitachi High-Tech Science Co., Ltd. ("TOF. SIMS5", manufactured by ION-TOF GmbH, Germany, measurement area: 550 μm square, primary ion source: Bi).

It is believed that the surface covered by the silicon oxide vapor deposition film of this invention can achieve the slipperiness and/or oleophobicity of grease or grease-containing components, therefore the thickness of the film will not have a particular effect. The thickness of the film is not particularly limited, preferably 1 nm to 800 nm, more preferably 5 nm to 500 nm, even more preferably 8 nm to 400 nm, even more preferably 10 nm to 300 nm, and most preferably 10 nm to 150 nm.

Furthermore, the thickness of the silicon oxide vapor-deposited film can be measured, for example, using a micro-spectral film thickness gauge (model: OPTM-A1) from Otsuka Electronics Co., Ltd., a micro-automatic film thickness measurement system (model: F54 XY 200UV) from Filmetrics Co., Ltd., a stylus film thickness gauge "DEKTAK" from Bruker, or by fabricating a cross-section of the film and using an electric field emission type operated motor microscope "JSM-7800F Prime" (30,000x magnification, 2 kV accelerating voltage, 10.3 mm working distance) from NEC Corporation.

[Molded Article] The molded article of this invention is a molded article whose surface is coated with the aforementioned silicon oxide vapor deposition film. The surface coating may be all or part of the inner and outer surfaces of the molded article, but for the purpose of content drainage, it preferably refers to the coating of the inner surface of the molded article. Furthermore, the surface refers to the outermost layer of the molded article. Additionally, the silicon oxide vapor deposition film of this invention may also have other films between the substrate of the coated molded article and the coating layer based on this invention.

The molded article (substrate) of this invention is preferably formed from a material selected from the group consisting of resin, glass, metal and paper. By having the silicon oxide vapor deposited film on the surface of the molded article, a molded article endowed with prevention of grease stains and improved oil removal properties can be obtained. Suitable resins include well-known thermoplastic resins such as low-density polyethylene, high-density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, polyolefins (e.g., random or block copolymers of α-olefins such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene), ethylene-vinyl compound copolymers (e.g., ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, ethylene-vinyl chloride copolymers, etc.), and styrene-based resins (e.g., polystyrene, acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene). Styrene (ABS), α-methylstyrene-styrene copolymer, etc.; polyvinyl chloride (e.g., polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinylidene chloride copolymer, polymethyl methacrylate, polymethyl methacrylate, etc.); polyamide (e.g., nylon 6, nylon 6-6, nylon 6-10, nylon 11, nylon 12, etc.); thermoplastic polyester (e.g., polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.); polycarbonate, polyphenylene oxide, polylactic acid, and other biodegradable resins, or mixtures thereof. Polyethylene, polyethylene terephthalate, and other resins are preferred. In addition, as a metal, it is preferred to be one or more metals selected from iron, nickel, copper, zinc, lead, aluminum, chromium, titanium, etc., or an alloy containing one or more of the metals as the main components, and more preferably stainless steel.

These molded articles can be films, sheets, pipes, containers, etc., and can also be cooking utensils. As pipes, examples include tubes, valves, and nozzles. As containers, examples include bottles, jars, cups, bags, plates, and also caps and nozzles. As cooking utensils, examples include ladles, mesh strainers, stoves, microwave ovens, and also kitchen exhaust fans and cooking counters. Molded articles such as bottles, jars, valves, and nozzles for use with oils are particularly preferred. Furthermore, oils are preferably for edible purposes. Furthermore, the portion of the molded article covered by the silicon oxide vapor deposition film can be all or part of the molded article, and in particular, it can be only the surface portion in contact with grease or grease-containing components.

The contact angle of refined rapeseed oil on the surface of the molded article of the present invention covered by the silicon dioxide vapor-coated film at 20°C is preferably 25° or more, more preferably 30° to 70°, further preferably 35° to 60°, and most preferably 33° to 55°.

(Slip property of grease or grease-containing components) Regarding the molded articles of the present invention, the slip property of grease or grease-containing components on the surface covered by the silicon oxide vapor-coated film, measured under the following conditions, is, for example, within 300 seconds, preferably within 60 seconds, more preferably within 20 seconds, and even more preferably within 10 seconds, with shorter times being better. For example, the slip property of grease or grease-containing components can be judged as good slip property of grease or grease-containing components in the order of more than 60 seconds to 300 seconds, more than 20 seconds to 60 seconds, more than 10 seconds to 20 seconds, and less than 10 seconds. Slip property of oils or oil-containing components: The time (in seconds) for the trailing end of an oil droplet (or liquid droplet) such as 24 ± 0.5 mg of rapeseed oil to travel 6 mm across the sample surface at 23 ± 3 °C on a sample surface tilted at 70° relative to a lead. Here, slip property can also be measured for oils or all products containing oils (oil-containing components). In this specification, when "oil" is mentioned, it refers not only to liquid oils, but also to oils and all products containing oils (oil-containing components). For example, "oil" in oleophobicity refers not only to oils or oils, but also to the oleophobicity of the oil component in oil-containing components. The oleophobicity of oil-containing components, such as seasonings, can be evaluated by the amount of oil-containing component discharged from the container (residual liquid). Furthermore, in this instruction manual, the terms "oil," "grease," and "oil-containing composition" are interchangeable. The measurement is performed using the rear end of an oil droplet (or liquid droplet) such as rapeseed oil, i.e., the uppermost contact point between the sample surface and the oil droplet (or liquid droplet) on the inclined sample surface, as a reference. Rapeseed oil can be dropped onto a sample surface inclined at 70° relative to the lead, or it can be dropped onto a horizontally positioned sample surface, and then measured at 70° relative to the lead. The sample being measured can be a storage container for grease or grease-containing components. Measurement can be performed directly, or a smooth portion of the storage container can be cut to create a flat or roughly flat sample for measurement. The method of tilting the sample at a 70° angle relative to the lead can be employed using known methods, such as the "stage AG85 (angle tilt)" manufactured by AS ONE Co., Ltd.

The oil, for example, is rapeseed oil, which is dripped onto the surface of a sample container used for storing oils or oil-containing components. Refined rapeseed oil, rapeseed oil sold for edible purposes, or rapeseed oil sold as a reagent can be used. Rapeseed oil sold for edible purposes can be rapeseed oil that conforms to the JAS (Japanese Agricultural Standard) standard ("Japanese Agricultural Standard for Edible Vegetable Oils," Ministry of Agriculture, Forestry and Fisheries Notice No. 681, August 19, 2019) as "Edible Rapeseed Oil," "Refined Rapeseed Oil," or "Rapeseed Salad Oil." For example, "Nisshin Canola Oil" (manufactured by Nisshin OilliO Group Co., Ltd.) can be used. Additionally, rapeseed oil (manufactured by Fujifilm and Koko Pure Pharmaceutical Co., Ltd.: Wako Grade 1) can be used as a reagent. Furthermore, oil-soluble colorants can be added to improve the visibility of rapeseed oil. For example, approximately 0.1% by weight of beta-carotene can be added to rapeseed oil. This level of beta-carotene addition has no substantial effect on the slippage value of the oil itself (the slippage value of the oil does not substantially change due to the presence or absence of beta-carotene). Refined rapeseed oil typically contains 51%–66% by weight of oleic acid, 19%–28% by weight of linolenic acid, 2%–11% by weight of hypolinolenic acid, 3%–6% by weight of palmitic acid, and 1%–3% by weight of stearic acid. The amount of the oil mixture added is 24 ± 0.5 mg, preferably 1 drop (approximately 24.36 mg) using a commercially available dropper. Alternatively, when storing the oil-containing composition in a container, various oil-containing compositions such as emulsified condiments (including mayonnaise and mayonnaise-type condiments), separated condiments, etc., can be used instead of oils, and the slip properties can be measured in the same manner as described above.

[Manufacturing Method of Molded Articles] The molded articles of this invention can be manufactured by using plasma CVD with organosilicon compounds and any oxidizing gas as the reaction gas, and coating the molded articles with a silicon oxide vapor deposition film.

(Organic silicon compounds and oxidizing gases) In the manufacturing method of the molded article of the present invention, organosilicone compounds are used as silicon sources for forming silicon oxide vapor deposits. As the organosilicone compound, the following can be used: organosilane compounds (e.g., hexamethyldisilane, vinyltrimethylsilane, methylsilane, dimethylsilane, tetramethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, methyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane, etc.) and organosiloxane compounds (e.g., 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 organosilicone compounds can be used alone or in combination of two or more. Furthermore, silanes ( _SiH₄ ) or silicon tetrachloride can be used in conjunction with the aforementioned organosilicone compounds. Preferably, the organosilicone compound has a functional group selected from methyl, methoxy, ethyl, or ethoxy as the organic functional group it possesses; more preferably, it is an organosilicone compound having ethoxy and/or methoxy groups; and even more preferably, it is an organosilicone compound having only ethoxy groups. Furthermore, it is also more preferably an organosilicone compound having only methyl groups. Preferred are tetraethoxysilane, tetramethoxysilane, hexamethyldisilazane, hexamethyldisilazane, etc., more preferably hexamethyldisilazane alone or organosilicone compounds containing hexamethyldisilazane. Furthermore, the organosilicone compound is preferably fluorine-free.

As an oxidizing gas, oxygen or NOx is used, with oxygen being preferred. Furthermore, as a carrier gas or a gas used for stabilizing discharges, rare gases such as argon or helium are used.

Regarding the manufacturing method of the molded article of the present invention, it is preferably a plasma CVD method in which the ratio of the flow rate (capacity) of the oxidizing gas to the total flow rate (capacity) of the reactant gas is 0% to 95% by capacity, and the molded article is coated with a silicon oxide vapor deposition film. By setting these conditions, a silicon oxide vapor deposition film with particularly excellent slippage and/or oleophobicity of grease or grease-containing components can be produced. The ratio of the flow rate (capacity) of the oxidizing gas to the total flow rate (capacity) of the reactant gas is more preferably 1% to 65% by capacity or 0% to 60% by capacity, more preferably 2% to 40% by capacity or 0% to 30% by capacity, and most preferably 5% to 10% by capacity. Furthermore, the flow rate of the reactant gas also depends on the area of the molded article to be treated. For example, when coating the inner surface of a plastic container with a capacity of 200 mL to 1.5 L, it is preferable to supply a flow rate of 3 sccm to 2000 sccm, especially 5 sccm to 600 sccm, per container. Moreover, "sccm" refers to the amount of gas (cc or ml) flowing within 1 minute at 0°C and 1 atmosphere.

(Plasma CVD) In this invention, a substrate surface held in a plasma processing chamber is subjected to plasma CVD treatment in an environment containing the aforementioned organosilicon compound, any oxidizing gas, and a carrier gas as needed, to form a vapor-deposited film of the aforementioned composition.

During plasma treatment, in order to maintain the plasma treatment chamber at a vacuum level sufficient for photoluminescence discharge, the pressure during film formation is preferably set to 1 Pa to 200 Pa, more preferably 3 Pa to 100 Pa. Under these conditions, a silicon oxide vapor deposition film is formed by supplying photoluminescence discharge with microwaves (300 MHz to 300 GHz) or high-frequency waves (1 MHz to 300 MHz). For example, the microwave output is preferably in the range of 10 W to 1000 W, more preferably 20 W to 1000 W. The microwave frequency is preferably 500 MHz to 30 GHz, more preferably 1 GHz to 10 GHz. The high-frequency output is preferably 20 W to 1500 W, more preferably 30 W to 1500 W. The preferred frequency for high-frequency waves is 1 MHz to 100 MHz, more preferably 1 MHz to 30 MHz, and even better 10 MHz to 15 MHz.

Furthermore, in the manufacturing method of the molded article of the present invention, as long as the outermost layer of the molded article is a silicon dioxide vapor-deposited film coated under the aforementioned conditions, the coating can also be performed on molded articles coated under other conditions under the aforementioned manufacturing conditions. Additionally, the conditions of the plasma CVD method can be altered by changing the amount of oxidizing gas supplied, and the coating can ultimately be performed under the aforementioned manufacturing conditions. [Example]

The present invention will now be described in more detail with examples, comparative examples, and reference examples, but the invention is not limited by these examples. Furthermore, unless otherwise specified, "%" represents mass percentage. Furthermore, in the table, "AO/B" refers to "ionic strength AO/ionic strength B", "AO/A" refers to "ionic strength AO/ionic strength A", "(A+AO)/S" refers to "(ionic strength A+ionic strength AO)/ionic strength S", "AO/S" refers to "ionic strength AO/ionic strength S", "A/S" refers to "ionic strength A/ionic strength S", and "R/A" refers to "ionic strength R/ionic strength A".

[Analytical Methods] (Surface Functional Group Analysis) The surfaces of the silicon oxide vapor-deposited samples of the embodiments and comparative examples were analyzed using a time-of-flight secondary ion mass analyzer (“TOF. SIMS5”, a product sold by Hitachi High-Tech Science Co., Ltd., accelerating voltage 30 kV, measuring area: 500 μm square, primary ion source: Bi). Based on the obtained ionic intensities of the wave peaks, calculate the ratio of ionic intensity AO to ionic intensity B (ionic intensity AO/ionic intensity B), the ratio of ionic intensity AO to ionic intensity A (ionic intensity AO/ionic intensity A), and the ratio of the sum of ionic intensity A and ionic intensity AO to ionic intensity S (ionic intensity S/ionic intensity B). Ionic strength (A + Ionic Intensity AO) / Ionic Intensity S, the ratio of ionic intensity AO to ionic intensity S (ionic intensity AO / ionic intensity S), the ratio of ionic intensity A to ionic intensity S (ionic intensity A / ionic intensity S), and the ratio of ionic intensity R to ionic intensity A (ionic intensity R / ionic intensity A). Furthermore, the ionic intensity (ionic strength) mentioned here is a value dependent on the number of ions detected using time-of-flight secondary ionic mass analysis (a value detected for each ion at each m/z). Ionic intensity S is defined as the intensity of a positive ion with m/z of 43.97. Ionic intensity A is defined as the sum of the intensities of positive ions with m/z of 43.00, m/z of 59.03, and m/z of 73.05. Ionic intensity AO is defined as the sum of the intensities of negative ions with m/z of 31.02 and m/z of... The sum of the intensities of the negative ion with m/z of 59.00, the negative ion with m/z of 74.99, the positive ion with m/z of 102.97, and the negative ion with m/z of 134.96 is used to define ionic intensity B as the sum of the intensities of the positive ions with m/z of 78.99 and m/z of 138.95. Ionic intensity R is defined as the sum of the intensities of the positive ions with m/z of 29.04 and m/z of 55.06.

(Film Thickness) The film thickness of the silicon oxide vapor-deposited films in the examples and comparative examples was measured using a microspectroscopic film thickness meter (model: OPTM-A1) from Otsuka Electronics Co., Ltd. A 20x reflective lens was used, and the measurement point was set to 10 μm.

(Contact Angle) The contact angle was measured using a contact angle meter ("DMo-502", manufactured by Kyowa Interface Science Co., Ltd.), using the "Contact Angle Measurement [Droplet Method]" setting. The liquid used for contact angle measurement was refined rapeseed oil ("Nisshin canola oil", manufactured by Nisshin OilliO Group Co., Ltd.), with a volume of 2.0 μL used per measurement. Furthermore, the grease in the contact angle meter was supplied using a "Teflon (registered trademark) coating needle" (manufactured by Kyowa Interface Science Co., Ltd.). Due to the high viscosity of the oil, it takes time for the liquid to wet and diffuse after being applied to the silicon oxide vapor-coated sample surfaces of both the exemplary and comparative examples. Therefore, the contact angle was recorded 50 seconds after application, when it had stabilized to a certain extent. The θ/2 method was used in the analysis (the radius r and height h of the droplet were determined by image processing, and then calculated using θ = 2arctan(h/r)).

(Oil Slipperiness) Prepare an oil storage container (polyethylene terephthalate (PET) container: 600 g capacity, with an inner diameter of 30.3 mm at the top opening and a height of 218.7 mm). Cut a 2 cm square PET plate from the flat part of the storage container before filling with oil. Using a dropper, drip 1 drop (approximately 24.36 mg) of refined rapeseed oil ("Nisshin canola oil" manufactured by Nisshin OilliO Group Co., Ltd., 99.9%) colored with carotene ("β-Carotene 30% FS"). The sample was immediately placed on a stage (manufactured by AS ONE Co., Ltd.) tilted at 70° relative to the vertical direction. The time it took for the rear end of the grease drop (the uppermost contact point between the sample surface and the grease drop on the tilted evaluation sample surface) to move 6 mm across the sample surface was measured. Furthermore, the temperature during measurement was room temperature (23°C). Evaluation was performed based on criteria A to E below using the movement time. If the criteria are A to D, the grease exhibits good slippage and/or oleophobic effect. It can be determined that the shorter the movement time, the higher and better the grease's slippage and/or oleophobic effect. A rating: Under 10 seconds B rating: Over 10-20 seconds C rating: Over 20-60 seconds D rating: Over 60-300 seconds E rating: Over 300 seconds

(Ratio of reduction in residual oil content) Prepare oil storage containers for both the embodiment and the comparative example as container samples. When the container sample is a filled PET sample (a container sample made by filling rapeseed oil or the like into a polyethylene terephthalate container coated with silicon oxide vapor-coated film as described later, and then sealing it), remove the lid, open the top opening of the container, and quickly tilt the container at a 160° angle relative to the plumb line to drain the rapeseed oil. In the case of a container sample that is a pillow-shaped container (a container sample formed by shaping a silicon dioxide vapor-coated film sample into a pillow shape, filling it with rapeseed oil, etc., and then sealing it), the heat-sealed portion of the opening is cut, and after opening the top opening of the container, the container is quickly tilted at a 180° angle relative to the plumb line to discharge the rapeseed oil. The time from the start of rapeseed oil discharge from the top opening of the container is set to 0 seconds. After 600 seconds, the tilt is restored to its original state, and the amount of rapeseed oil remaining in the container (residual oil amount) is measured. The test is conducted at room temperature (23°C). When the amount of residual grease in the grease storage container of Comparative Example 1 or Comparative Example 8 is set as B (mass %), and the amount of residual grease in the grease storage containers of other embodiments or comparative examples is set as A (mass %), the reduction percentage of the residual grease amount is calculated according to the following formula: Reduction percentage of residual grease amount (%) = (1 - A/B) × 100

(Residual Amount of Seasoning) Oil storage containers from the embodiments and comparative examples were prepared as container samples. After mixing by inversion 100 times with the lid on, the lid was removed, and the top opening of the container was opened, causing the container to be rapidly tilted at a 160° angle relative to a plumb line to drain the internal solution (the seasoning that had been filled in). The time it took for the internal solution to begin draining from the top opening of the container was set to 0 seconds. After 600 seconds, the tilt was returned to its original position, and the amount of internal solution remaining in the container (residual amount) was measured. The test was conducted at room temperature (23°C). When the residual liquid content of the grease storage container in Comparative Example 1 is set as D (mass %), and the residual liquid content of the grease storage containers in all other embodiments is set as C (mass %), the reduction percentage of the residual liquid content is calculated according to the following formula: Reduction percentage of residual liquid content (%) = (1 - C/D) × 100

[Comparative Examples and Embodiments] (Plasma CVD Apparatus 1) The film formation conditions of the plasma CVD apparatus 1 used in Comparative Examples 2 to 6 and Embodiments 1 to 5 are shown in Table 1. Furthermore, the settings of the plasma CVD apparatus 1 other than those in Table 1 are described below. Name: Plasma CVD Unit 1 Film Formation Method: Plasma Enhanced Chemical Vapor Deposition (PECVD) Plasma Source: Capacitively Coupled Plasma (CCP) Electrode Shape: Similar type (relative to container shape) External Radio Frequency (RF) Electrode: Two-piece structure, no cooling mechanism Internal Gas Inlet Electrode: ø6.35 mm, no heating mechanism Material: Aluminum alloy (external electrode), steel use stainless steel (SUS) 304 (internal electrode) RF Power Supply: Frequency 13.56 MHz RF Switch: 2-channel Matching Method: Automatic impedance matching Exhaust Structure: Mechanical booster pump (main suction), rotary pump (auxiliary) Exhaust Manifold External Dimensions: 350 mm × 350 mm × H150 mm

(Plasma CVD Apparatus 2) The film formation conditions of the plasma CVD apparatus 2 used in Comparative Example 7, Examples 6, and Examples 7 are shown in Table 8. Regarding the plasma CVD apparatus 2, the configuration is the same as that of the plasma CVD apparatus 1, except that the electrode portion of the plasma CVD apparatus 1 is changed to parallel plate electrodes (electrode spacing 50 mm, upper gas spray electrode: made of aluminum alloy and SUS304, heated type, ø320 mm, lower RF electrode: made of SUS304, water-cooled type, ø320 mm). Furthermore, the first electrode does not serve as the plasma processing chamber; instead, the structure of the first and second parallel plate electrodes is arranged within the plasma processing chamber.

<Experiment 1> (Preparation of silicon oxide vapor-coated film and molded article 1) For uncoated commercially available polyethylene terephthalate containers for edible oils (PET container: bottle shape, capacity 600 g, inner diameter of the opening at the top 30.3 mm, height 218.7 mm, Comparative Example 1), plasma treatment was performed in an organosilicone compound environment under the film-forming conditions in Table 1 using a plasma CVD apparatus 1 (details as described above), thereby coating the PET container with a silicon oxide vapor-coated film, serving as container samples (oil storage containers) for Comparative Examples 2 to 6 and Examples 1 to 4. In the container samples of Comparative Examples 2 to 6 and Examples 1 to 4, specifically, tetraethoxy silane (hereinafter, sometimes referred to as TEOS), tetramethoxy silane (hereinafter, sometimes referred to as TMOS), or hexamethyl disiloxane (hereinafter, sometimes referred to as HMDSO) were used as organosilicone compounds. Oxygen ( _O₂ ) was mixed with the organosilicone compounds as an oxidizing gas as needed, and used as a reaction gas. Additionally, helium (He) was used as the carrier gas for TEOS, and argon (Ar) was used as a discharge stabilizing gas, as needed. First, the uncoated PET container is placed in the plasma processing chamber of the plasma CVD apparatus 1. After reducing the pressure in the plasma processing chamber to below 1 Pa, the reaction gas, any carrier gas, and discharge stabilizing gas are introduced into the plasma processing chamber at the flow rates recorded in Table 1. After stabilizing to the pressure recorded in Table 1 for 30 to 60 seconds, discharge is performed for the time recorded in Table 1 at the plasma output recorded in Table 1, coating the surface of the PET container with a silicon oxide vapor deposition film. After discharge, the introduction of the reaction gas, any carrier gas, and discharge stabilizing gas is stopped. After reducing the pressure in the film formation chamber to below 1 Pa, the plasma processing chamber is released to the atmosphere, and the PET container is removed from the plasma processing chamber.

A filled PET sample (container sample) was prepared by filling 600 g of refined rapeseed oil (Nisshin canola oil, manufactured by Nisshin OilliO Group Co., Ltd.) into a PET container coated with a silicon dioxide vapor-coated film, and then sealing it. The amount of residual oil and the percentage reduction in residual oil content of the container sample were measured. Additionally, a 2 cm square PET plate was cut from the flat portion of the PET container (container sample) coated with the silicon dioxide vapor-coated film, and the ionic strength and its proportion, film thickness, contact angle, and oil slippage were analyzed and evaluated according to the contents, and the results are shown in Table 2. Furthermore, the container sample was subjected to either Preservation Test 1 or Preservation Test 2 to determine the reduction rate of residual grease (see "Residual Grease Amount" and "Reduction Rate of Residual Grease Amount" in Tables 3 (Preservation Test 1) and 4 (Preservation Test 2)). In addition, the container after the reduction rate of residual grease was determined was cut, and the contact angle and grease slippage of the un-grease-adhered portion were measured according to the aforementioned methods. Furthermore, the contact angle was measured after cleaning and drying with hexane. These results are shown in Tables 3 (Preservation Test 1) and 4 (Preservation Test 2).

(Preservation Test 1: Accelerated Test) Approximately 600 g of refined rapeseed oil (manufactured by Nisshin OilliO Group Co., Ltd.) was filled into the container samples of Comparative Examples 1-6 and Examples 1-4. The containers were then sealed. The sealed container samples containing the refined rapeseed oil were stored in a dark place at 60°C for 8 weeks. Furthermore, the chemical reaction was accelerated by approximately two times when the temperature increased by 10°C. Therefore, the result of the accelerated test at 60°C for 8 weeks is equivalent to the result after storage at room temperature (20°C) for 128 weeks (8 weeks × 16).

(Preservation Test 2: Exposure Test) The sealed container containing refined rapeseed oil was stored at 20°C under 1,000 Lux light for 6 weeks.

[Table 1] Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Implementation Example 1 Implementation Example 2 Implementation Example 3 Implementation Example 4 raw material - TEOS TEOS TMOS HMDSO HMDSO HMDSO HMDSO HMDSO HMDSO Raw material flow rate [sccm] - 53.8 10.8 10 20 50 50 50 50 10 Oxygen flow rate [sccm] - 0 50 0 200 500 50 500 50 0 Ar flow rate [sccm] - 0 0 0 0 0 0 0 0 50 He flow rate [sccm] - 100 100 0 0 0 0 0 0 0 Pressure [Pa] - 10 10 20 10 30 30 30 30 50 Plasma output [W] - 100 100 100 300 1000 1000 100 100 100 time [seconds] - 15 15 10 10 2 2 10 10 10

[Table 2] Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Implementation Example 1 Implementation Example 2 Implementation Example 3 Implementation Example 4 AO strength - 4816 399 28278 28459 36074 48850 43251 63565 39829 Strength of A - 4349 13758 9615 63693 76267 118862 85475 204187 310300 The strength of B - 52730 10042 1679 2442 1413 482 708 223 3.0 The strength of S - 618 11305 1503 1990 1423 700 931 585 8.5 The strength of R - 65770 17887 2331 1810 1933 1518 895 577 221 AO/B - 0.1 0.0 16.8 11.7 25.5 101.5 61.1 285.7 13276.3 AO/A - 1.11 0.03 2.94 0.45 0.47 0.41 0.51 0.31 0.13 (A+AO)/S - 14.8 1.3 25.2 46.3 79.0 239.6 138.3 457.7 41191.6 AO/S - 7.8 0.0 18.8 14.3 25.4 69.8 46.5 108.7 4685.8 A/S - 7.0 1.2 6.4 32.0 53.6 169.8 91.9 349.0 36505.8 R/A - 15.1 1.3 0.2 0.0 0.0 0.0 0.0 0.0 0.0 Film thickness - 253.3 72.3 10.1 195.3 85.4 122.6 91.5 12.3 253.3 Remaining oil (after 600 seconds) 1.53 g 0.11 g 0.61 g 0.29 g 0.21 g 0.35 g 0.32 g 0.21 g 0.13 g 0.13 g The percentage of remaining oil compared to Comparative Example 1 (the percentage decrease in remaining oil content). - (-) 7.2% (92.8%) 39.9% (60.1%) 19.0% (81.0%) 13.7% (86.3%) 22.9% (77.1%) 20.9% (79.1%) 13.7% (86.3%) 8.5% (91.5%) 8.5% (91.5%) Contact angle (°) Below 7 41.6 17.8 28.9 42.1 41.9 43.4 47.0 50.1 53.6 Oil slippage (seconds) More than 300 5 18 7 8 10 8 6 5 5 Evaluation E A B A A A A A A A

[Table 3] Preservation Experiment 1 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Implementation Example 1 Implementation Example 2 Implementation Example 3 Implementation Example 4 Remaining oil (after 600 seconds) 1.55 1.39 1.43 1.46 1.45 1.58 0.41 0.13 0.22 0.12 The percentage of remaining oil compared to Comparative Example 1 (the percentage decrease in remaining oil content). - (-) 89.7% (10.3%) 92.3% (7.7%) 94.2% (5.8%) 93.6% (6.4%) More than 100% (0%) 26.5% (73.5%) 8.4% (91.6%) 14.2% (85.8%) 7.7% (92.3%) Contact angle (°) Below 7 7.2 18.2 13.6 26.5 21.0 38.5 38.3 49.0 55.2 Oil slippage (seconds) More than 300 107 69 259 69 More than 300 12 27 7 6 Evaluation E D D D D E B C A A

[Table 4] Preservation Experiment 2 Comparative example 1 Comparative example 2 Comparative example 4 Comparative example 5 Comparative example 6 Implementation Example 1 Implementation Example 2 Implementation Example 3 Implementation Example 4 Remaining oil (after 600 seconds) 1.55 1.35 1.42 1.41 1.47 0.36 0.74 0.33 0.14 The percentage of remaining oil compared to Comparative Example 1 (the percentage decrease in remaining oil content). - (-) 87.1% (12.9%) 91.6% (8.4%) 91.0% (9.0%) 94.8% (5.2%) 23.2% (76.8%) 47.7% (52.3%) 21.3% (78.7%) 9.0% (91.0%) Contact angle (°) Below 7 22.7 10.3 32.4 30.8 41.5 43.5 50.4 52.9 Oil slippage (seconds) More than 300 162 More than 300 65 More than 300 10 10 6 9 Evaluation E D E D E A A A A

<Experiment 2> (Preparation of Silicon Oxide Evaporated Film and Molded Article 2) A commercially available polyethylene terephthalate (PET) container for edible oils (PET container: bottle-shaped, capacity 600 g, inner diameter of the opening at the top 30.3 mm, height 218.7 mm, Comparative Example 1) without coating was subjected to plasma treatment using a plasma CVD apparatus 1 (details as described above) under the film-forming conditions in Table 5, similar to the preparation of the silicon oxide evaporated film and molded article 1. This resulted in the coating of the PET container with a silicon oxide evaporated film, serving as container samples (oil storage containers) for Examples 4 and 5. Furthermore, the container samples of Comparative Example 1 and Example 4 were manufactured under the same conditions as in Experiment 1.

The reduction rate of residual liquid was measured by filling 600 g of emulsified seasoning (commercially available product name "Nisshin dressing diet - Rich Sesame Flavor", manufactured by Nisshin OilliO Group Co., Ltd.: 12% by weight of oil (liquid oil form)) or separated seasoning (commercially available product name "Nisshin dressing diet - Sweet Japanese Style", manufactured by Nisshin OilliO Group Co., Ltd.: 12% by weight of oil (liquid oil form)) into the PET container (container sample) coated with a silicon oxide vapor-coated film. The results are shown in Table 6. Furthermore, the following preservation test 3 was performed on the container sample to measure the reduction rate of residual liquid. The results are shown in Table 7 (Preservation Experiment 3).

(Preservation Test 3: Accelerated Test of Seasoning) Approximately 600 g of the emulsified or separated seasoning was filled into the container samples of Comparative Example 1, Example 4, and Example 5. The containers were then capped and sealed. The sealed container samples containing the seasoning were stored in a dark place at 40°C for 16 weeks.

[Table 5] Comparative example 1 Implementation Example 4 Implementation Example 5 raw material - HMDSO HMDSO Raw material flow rate [sccm] - 10 50 Oxygen flow rate [sccm] - 0 0 Ar flow rate [sccm] - 50 50 He flow rate [sccm] - 0 0 Pressure [Pa] - 50 30 Plasma output [W] - 100 1000 time [seconds] - 10 2

[Table 6] Comparative example 1 Implementation Example 4 Implementation Example 5 AO strength - 39829 35104 Strength of A - 310300 162715 The strength of B - 3.0 177 The strength of S - 8.5 189 The strength of R - 221 1361 AO/B - 13276.3 198.3 AO/A - 0.13 0.22 (A+AO)/S - 41191.6 1046.7 AO/S - 4685.8 185.7 A/S - 36505.8 860.9 R/A - 0.0 0.0 Emulsified seasonings Residual liquid volume (after 600 seconds) 19.55 g 2.23 g 13.21 g The percentage of residual liquid relative to Comparative Example 1 (the percentage decrease in residual liquid volume). - (-) 11.4% (88.6%) 67.6% (32.4%) Separate seasonings Residual liquid volume (after 600 seconds) 3.17 g 0.77 g 1.18 g The percentage of residual liquid relative to Comparative Example 1 (the percentage decrease in residual liquid volume). - (-) 24.2% (75.8%) 37.2% (62.8%)

[Table 7] Preservation Experiment 3 Comparative example 1 Implementation Example 4 Implementation Example 5 Emulsified seasonings Residual liquid volume (after 600 seconds) 12.58 g 4.77 9.08 The percentage of residual liquid relative to Comparative Example 1 (the percentage decrease in residual liquid volume). - (-) 37.9% (62.1%) 72.2% (27.8%) Separate seasonings Residual liquid volume (after 600 seconds) 3.79 g 2.12 g 2.68 g The percentage of residual liquid relative to Comparative Example 1 (the percentage decrease in residual liquid volume). - (-) 55.9% (44.1%) 70.7% (29.3%)

<Experiment 3> (Preparation of Silicon Oxide Evaporated Film and Molded Article 3) Using uncoated commercially available mirror-polished (#800) stainless steel sheet (SUS304, 20 mm in length, 20 mm in width, 1 mm in thickness), plasma treatment was performed in an organosilicon compound environment under the film-forming conditions in Table 8, thereby coating the stainless steel sheet with a silicon oxide evaporated film, serving as stainless steel sheet samples for Comparative Example 7, Example 6, and Example 7. Specifically, in the stainless steel sheet samples of Comparative Example 7, Example 6, and Example 7, hexamethyldisiloxane (hereinafter sometimes referred to as HMDSO) was used as the organosilicon compound. Oxygen ( _O2 ) is mixed with the organosilicon compound as an oxidizing gas as needed, and used as a reaction gas. Additionally, argon (Ar) is used as a discharge stabilizing gas as needed. First, the uncoated stainless steel plate is placed in the plasma processing chamber of the plasma CVD apparatus 2. After reducing the pressure in the plasma processing chamber to below 5 Pa, the reaction gas and any discharge stabilizing gas are introduced into the plasma processing chamber at the flow rate recorded in Table 8. After stabilizing to the pressure recorded in Table 8 for 30 to 60 seconds, discharge is performed for the time recorded in Table 8 at the plasma output recorded in Table 8, resulting in a silicon oxide vapor deposition film being coated on the surface of the stainless steel plate. After discharge, the introduction of reaction gas and any discharge stabilizing gas is stopped. After the pressure in the film-forming chamber is reduced to below 5 Pa, the plasma treatment chamber is released to the atmosphere, and the stainless steel plate is removed from the plasma treatment chamber.

The ionic strength and ratio, contact angle, and grease slippage of the stainless steel plate sample coated with a silicon oxide vapor-deposited film according to the aforementioned content were analyzed and evaluated, and are shown in Table 9. Furthermore, the following preservation test 4 was performed on the stainless steel plate sample. On the ungreased portions, the contact angle and grease slippage were measured according to the aforementioned content. Moreover, the contact angle was measured after cleaning and drying with hexane. These results are shown in Table 10 (Preservation Test 4).

(Preservation Test 4: Heating Test) Approximately 2 kg of refined rapeseed oil ("Nisshin canola oil," manufactured by Nisshin OilliO Group Co., Ltd.) was filled into an electric deep fryer (Zojirushi Magic Bottle Co., Ltd., product number: EFK-A10). After adjusting the oil temperature to 180°C, stainless steel plate samples from Comparative Example 7, Examples 6, and Examples 7 were placed in the oil and stored for 30 minutes. Furthermore, the stainless steel plate samples were placed in a manner that prevented direct contact with the heat source.

[Table 8] Comparative example 7 Implementation Example 6 Implementation Example 7 raw material HMDSO HMDSO HMDSO Raw material flow rate [sccm] 10 50 50 Oxygen flow rate [sccm] 50 0 500 Ar flow rate [sccm] 0 50 0 He flow rate [sccm] 0 0 0 Pressure [Pa] 11 50 50 Plasma output [W] 300 100 300 time [seconds] 30 30 30

[Table 9] Comparative example 7 Implementation Example 6 Implementation Example 7 AO strength 22946 17206 58668 Strength of A 75977 207136 153529 The strength of B 3291 4 467 The strength of S 1488 302 814 The strength of R 5357 3700 1080 AO/B 7.0 4301.5 125.7 AO/A 0.30 0.08 0.38 (A+AO)/S 66.5 742.9 260.8 AO/S 15.4 57.0 72.1 A/S 51.1 685.9 188.7 R/A 0.1 0.0 0.0 Contact angle (°) 37.8 53.4 51.2 Oil slippage (seconds) 56 10 16 Evaluation C A B

[Table 10] Preservation Experiment 4 Comparative example 7 Implementation Example 6 Implementation Example 7 Contact angle (°) 17.6 54.8 35.0 Oil slippage (seconds) More than 300 17 31 Evaluation E B C

<Experiment 4> (Preparation of Silicon Oxide Evaporated Film and Molded Article 4) Uncoated polyethylene film (low-density polyethylene (PE) film: 120 μm thick) was cut into 20 cm squares as Comparative Example 8. Using the plasma CVD apparatus 2, in an organosilicon compound environment, under the film formation conditions in Table 11, the evaluation sample, which had been treated in the same manner as Comparative Example 8, was subjected to plasma treatment, thereby coating the polyethylene film using silicon oxide evaporation, as the film samples of Examples 8 and 9. Specifically, hexamethyldisiloxane was used as the organosilicon compound in the film samples of Examples 8 and 9. Oxygen ( _O2 ) is mixed with the organosilicon compound as an oxidizing gas as needed, and used as a reaction gas. Additionally, argon (Ar) is used as a discharge stabilizing gas as needed. First, the uncoated polyethylene film is placed in the plasma processing chamber of the plasma CVD apparatus 2. After reducing the pressure in the plasma processing chamber to below 5 Pa, the reaction gas and any discharge stabilizing gas are introduced into the plasma processing chamber at the flow rate recorded in Table 11. After stabilizing to the pressure recorded in Table 11 for 30 to 60 seconds, discharge is performed for the time recorded in Table 11 at the plasma output recorded in Table 11, and a silicon oxide vapor deposition film is coated onto the surface of the polyethylene film. After discharge, the introduction of reaction gas and any discharge stabilizing gas is stopped. After the pressure in the film-forming chamber is reduced to below 5 Pa, the plasma treatment chamber is released to the atmosphere, and the polyethylene film is taken out from the plasma treatment chamber.

The ionic strength and its proportion of the polyethylene film samples coated with silicon oxide vapor deposition were analyzed. The analysis results are shown in Table 12. Furthermore, the polyethylene film samples were shaped into pillows (dimensions: 10 cm wide, 20 cm high, opening size: 19 cm circumference), filled with 250 g of refined rapeseed oil ("Nisshin canola oil," manufactured by Nisshin OilliO Group Co., Ltd.), and the opening was sealed by heat sealing to produce multiple filled pillow samples. The reduction rate of residual oil content in the filled pillow samples was evaluated according to the following criteria. The evaluation results are shown in Table 12. Furthermore, the filled pillow samples were subjected to the following preservation test 5, and the reduction rate of residual oil content was evaluated according to the following criteria. The evaluation results are shown in Table 13.

(Preservation Test 5: Accelerated Test) The pillow samples from Comparative Example 8, Example 8, and Example 9 were stored in a dark place at 60°C for 8 weeks.

[Table 11] Implementation Example 8 Implementation Example 9 raw material HMDSO HMDSO Raw material flow rate [sccm] 40 10 Oxygen flow rate [sccm] 100 0 Ar flow rate [sccm] 0 50 He flow rate [sccm] 0 0 Pressure [Pa] 20 10 Plasma output [W] 100 100 time [seconds] 30 30

[Table 12] Comparative example 8 Implementation Example 8 Implementation Example 9 AO strength - 66492 226 Strength of A - - 27747 The strength of B - 18 9 The strength of S - 439 1 The strength of R - 4865 2 AO/B - 3799.5 26.6 AO/A - - 0.01 (A+AO)/S - - 27973.0 AO/S - 151.5 226.0 A/S - - 27747.0 R/A - - 0.0 Remaining oil (after 600 seconds) 1.17 g 0.27 g 0.23 g The percentage of residual oil compared to Comparative Example 8 (the percentage decrease in residual oil content). - (-) 23.1% (76.9%) 19.7% (80.3%)

[Table 13] Preservation Experiment 5 Comparative example 8 Implementation Example 8 Implementation Example 9 Remaining oil (after 600 seconds) 1.48 g 0.69 g 0.64 g The percentage of residual oil compared to Comparative Example 8 (the percentage decrease in residual oil content). - (-) 46.6% (53.4%) 43.2% (56.8%)

without

Claims (10)

A silicon oxide vapor deposition film, wherein, on the surface of the silicon oxide vapor deposition film, in the ionic intensities obtained by time-of-flight secondary ionic mass analysis, the ratio of ionic intensity AO to ionic intensity B (ionic intensity AO/ionic intensity B) is 26 or more, wherein, ionic intensity B is the sum of the intensities of positive ions with m/z of 78.99 and positive ions with m/z of 138.95, The ionic intensity AO is the sum of the intensities of the negative ions with m/z 31.02, m/z 59.00, m/z 74.99, m/z 102.97, and m/z 134.96. The silicon oxide vapor deposition film as described in claim 1, wherein the ratio of ionic intensity R to ionic intensity A (ionic intensity R/ionic intensity A) on the surface of the silicon oxide vapor deposition film, obtained by time-of-flight secondary ionic mass analysis, is 0.3 or less, (wherein, ionic intensity A is the sum of the intensities of positive ions with m/z of 43.00, m/z of 59.03, and m/z of 73.05; and ionic intensity R is the sum of the intensities of positive ions with m/z of 29.04 and m/z of 55.06). The silicon oxide vapor-deposited film as described in claim 1 or 2, wherein of the ionic intensities obtained using time-of-flight secondary ionic mass analysis on the surface of the silicon oxide vapor-deposited film, the ratio of ionic intensity AO to ionic intensity A (ionic intensity AO/ionic intensity A) is 0.1 or more, and/or the ratio of the sum of ionic intensity A and ionic intensity AO to ionic intensity S ((ionic intensity A + ionic intensity AO)/ionic intensity S) is 100 or more, and/or the ratio of ionic intensity AO to ionic intensity S (ionic intensity AO/ionic intensity S) is 30 or more, (wherein, ) The ionic strength S is the strength of a positive ion with m/z of 43.97. The ionic strength A is the sum of the strengths of the positive ions with m/z of 43.00, m/z of 59.03, and m/z of 73.05. The silicon oxide vapor-coated film as described in any one of claims 1 to 3, wherein the silicon oxide vapor-coated film exhibits a slip resistance of less than 300 seconds in the following oil slip resistance test when using rapeseed oil as the oil: Oil slip resistance: the time (in seconds) for the trailing end of an oil droplet of 24 ± 0.5 mg of rapeseed oil to move 6 mm across the surface of the silicon oxide vapor-coated film sample at 23 ± 3°C at a tilt of 70° relative to the lead. The silicon oxide evaporation film as described in any of claims 1 to 4, wherein the silicon oxide evaporation film is a film derived from hexamethyldisiloxane. A molded article having its surface covered with a silicon oxide vapor-coated film as described in any one of claims 1 to 5. The molded article as described in claim 6, wherein the molded article is a container, piping or cooking utensil formed from a material selected from resin, glass, metal, clay and paper. A method for manufacturing a molded article, said molded article being coated with the silicon oxide vapor deposition film, said manufacturing method comprising: (A) a step of preparing the molded article, and (B) a step of coating the surface of said molded article with the silicon oxide vapor deposition film as described in any one of claims 1 to 5. The manufacturing method as described in claim 8, wherein the coating is performed by plasma chemical vapor deposition using an organosilicon compound and any oxidizing gas as the reaction gas. The manufacturing method as described in claim 8 or 9, wherein the silicon oxide vapor-deposited film is a film derived from hexamethyldisiloxane.