Silicon oxide vapor-deposited film and molded article including same

Abstract

The purpose of the present invention is to provide: a silicon oxide vapor-deposited film having, at high levels, the function of repelling oil and / or the ability to slide off oil, fat, or an oil-or-fat-containing composition; and a molded article coated with a silicon oxide vapor-deposited film having, at high levels, the function of repelling oil and / or the ability to slide off oil or fat. Specifically, provided is a silicon oxide vapor-deposited film. Regarding ionic strengths obtained by a time-of-flight secondary ion mass spectrometry performed on the surface of the silicon oxide vapor-deposited film, the ratio (ionic strength AO / ionic strength B) of ionic strength AO to ionic strength B is 26 or more.

Description

Silicon oxide vapor deposition film and molded products containing it

[0001] The present invention relates to a silicon oxide vapor-deposited film and a molded article coated with the silicon oxide vapor-deposited film. In particular, the present invention relates to a silicon oxide vapor-deposited film that exhibits high sliding properties and / or oil-repellent properties for oils and fats or oil-containing compositions, and to a molded article containing the same.

[0002] Conventionally, films have been formed on the surfaces of various substrates to improve their properties. For example, in the case of packaging materials, vapor-deposited films are formed on the surfaces of plastic molded products by plasma CVD to improve their gas barrier properties.

[0003] For example, a method for manufacturing a plastic container is known in which the concentration of the organosilicon compound changes when a barrier layer (vapor-deposited film) containing silicon oxide and at least one compound consisting of at least one or more elements selected from carbon, hydrogen, silicon, and oxygen is formed on at least one side of the plastic container by plasma CVD using at least an organosilicon compound and oxygen or a gas having oxidizing power. The gas flow ratios of the organosilicon compound (hexamethyldisiloxane) and oxygen were 1:2, 1:20, and 1:100 (see Patent Document 1).

[0004] It has also been shown that a silicon oxide film produced at a flow rate ratio of an organosilicon compound gas to a gas containing oxygen atoms in the range of 1:3 to 50, and having a component ratio of 100 Si atoms to 170 to 200 O atoms and 30 or less C atoms, has gas barrier properties (see Patent Document 2).

[0005] On the other hand, for containers, cooking utensils, and the like, good cleanability and ease of content discharge after use improve workability and reduce environmental impact. Therefore, water and oil repellency are also required as characteristics of the substrate of containers, cooking utensils, and the like. For example, a bottle with good water repellency has been proposed in which an organic silicon compound film containing nitrogen, silicon, carbon, and hydrogen is formed, and then a silicon oxide compound film containing a silicon oxide compound as the main component is formed on the surface by a CVD method (a gas flow ratio of hexamethyldisiloxane and oxygen of 1:4) (see Patent Document 3). Molded products coated with a silicon oxide vapor-deposited film with good oil repellency have also been proposed (Patent Document 4). However, although the silicon oxide vapor-deposited film in Patent Document 4 has oil repellency, there is a problem in that the oil repellency deteriorates when the film comes into contact with oils and fats for a long period of time or at high temperatures. Therefore, sufficient research has not been conducted on a good silicon oxide compound film that maintains oil repellency for a long period of time or at high temperatures.

[0006] JP 2000-255579 A JP 2003-53873 A JP 2009-46162 A JP 2023-95740 A

[0007] An object of the present invention is to provide a silicon oxide vapor-deposited film that retains the ability to slide off fats and oil-containing compositions and / or oil-repellent properties even when in contact with fats and oil-containing compositions for a long period of time or at high temperatures, and further to provide a molded article coated with a silicon oxide vapor-deposited film that retains the ability to slide off fats and oil-containing compositions and / or oil-repellent properties even when in contact with fats and oil-containing compositions for a long period of time or at high temperatures.

[0008] As a result of extensive research, the present inventors have found that by using a silicon oxide vapor-deposited film containing a certain proportion of hydroxyl groups and alkoxy groups, it is possible to obtain a coating that has high oil- and fat-containing composition sliding properties and / or oil-repellency even when in contact with oils and fats or oil- and fat-containing compositions for a long period of time or at high temperatures, and a molded article having such a coating, and have completed the present invention.

[0009] That is, one aspect of the present invention may relate to the following: [1] A silicon oxide vapor-deposited film, wherein the surface of the silicon oxide vapor-deposited film has an ionic strength AO ratio to ionic strength B (ionic strength AO / ionic strength B) of 26 or more, as determined by time-of-flight secondary ion mass spectrometry. (wherein ionic strength B is the sum of the ionic strengths of the positive ions at m / z 78.99 and the positive ions at m / z 138.95, and ionic strength AO is the sum of the ionic strengths of the negative ions at m / z 31.02, the negative ions at m / z 59.00, the negative ions at m / z 74.99, the positive ions at m / z 102.97, and the negative ions at m / z 134.96). [2] The silicon oxide vapor-deposited film according to [1] above, wherein the surface of the silicon oxide vapor-deposited film has an ionic strength R to ionic strength A ratio (ionic strength R / ionic strength A) of 0.3 or less in ionic strengths measured by time-of-flight secondary ion mass spectrometry. (wherein ionic strength A is the sum of the ionic strengths of the positive ions at m / z 43.00, m / z 59.03, and m / z 73.05, and ionic strength R is the sum of the ionic strengths of the positive ions at m / z 29.04 and m / z 55.06). [3] The silicon oxide vapor-deposited film according to [1] or [2] above, wherein, in ionic strengths measured by time-of-flight secondary ion mass spectrometry, the surface of the silicon oxide vapor-deposited film has a ratio of the ionic strength AO to the ionic strength A (ionic strength AO / ionic strength A) of 0.1 or more, and / or a ratio of the sum of the ionic strength A and the ionic strength AO to the ionic strength S ((ionic strength A+ionic strength AO) / ionic strength S) of 100 or more, and / or a ratio of the ionic strength AO to the ionic strength S (ionic strength AO / ionic strength S) of 30 or more. (wherein ionic strength S is the strength of the positive ion at m / z 43.97, and ionic strength A is the sum of the intensities of the positive ions at m / z 43.00, m / z 59.03, and m / z 73.05). [4] The silicon oxide vapor deposition film according to any one of [1] to [3] above, wherein the silicon oxide vapor deposition film has a sliding property of 300 seconds or less in the following oil sliding property test using rapeseed oil as the oil.Sliding property of oil and fat: The time (seconds) required for the rear end of a 24±0.5 mg rapeseed oil droplet to move 6 mm on the surface of a silicon oxide vapor-deposited film sample tilted at 70° to the vertical at 23±3°C. [5] The silicon oxide vapor-deposited film according to any one of [1] to [4] above, wherein the silicon oxide vapor-deposited film is a film derived from hexamethyldisiloxane. [6] A molded product whose surface is coated with the silicon oxide vapor-deposited film according to any one of [1] to [5] above. [7] The molded product according to [6] above, wherein the molded product is a container, pipe, or cookware molded from a material selected from resin, glass, metal, china clay, and paper. [8] A method for producing a molded product coated with the silicon oxide vapor-deposited film, comprising: (A) a step of preparing a molded product; and (B) a step of coating the surface of the molded product with the silicon oxide vapor-deposited film according to any one of [1] to [5] above. [9] The method according to [8], wherein the coating is performed by a plasma CVD method using an organosilicon compound and an arbitrary oxidizing gas as reactive gases.

[10] The method according to [8] or [9], wherein the silicon oxide vapor-deposited film is a film derived from hexamethyldisiloxane.

[0010] According to the present invention, a silicon oxide vapor-deposited film can be provided that exhibits excellent oil-repellency and / or slippage 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. When exposed to oil for a long period of time, the film can maintain its function for a long period of time, for example, at temperatures of 100°C or below or 60°C or below, for 8 weeks or more, and at temperatures of 40°C or below, near room temperature (23°C ± 3°C), for 128 weeks. Furthermore, the film can maintain its heat resistance (high-temperature durability) at temperatures of 100 to 250°C or 150 to 200°C. Furthermore, molded articles coated with the silicon oxide vapor-deposited film are expected to be easily stained and have good cleanability against oily stains. Furthermore, when the molded article is a container, piping, or the like, it is expected to have good oil drainage and little residual oil.

[0011] The present invention will be described in detail below by way of example. In the embodiments of the present invention, A (numerical value) to B (numerical value) means A or more and B or less. The preferred and more preferred embodiments exemplified below can be used in appropriate combinations with each other, regardless of expressions such as "preferable" or "more preferred." Furthermore, the descriptions of numerical ranges are merely examples, 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 expressions such as "preferable" or "more preferred." Furthermore, terms such as "contain" or "comprise" may be interpreted as "essentially consisting of" or "consisting only of," as appropriate.

[0012] [Silicon oxide vapor-deposited film] The silicon oxide vapor-deposited film of the present invention is a silicon oxide vapor-deposited film whose surface has, in ionic strengths measured by time-of-flight secondary ion mass spectrometry, (a) a ratio of ionic strength AO to ionic strength B (ionic strength AO / ionic strength B) of 26 or more. The silicon oxide vapor-deposited film of the present invention is preferably a silicon oxide vapor-deposited film in which, in ionic strength measurements obtained by time-of-flight secondary ion mass spectrometry, the surface of the silicon oxide vapor-deposited film has (b) a ratio of ionic strength R to ionic strength A (ionic strength R / ionic strength A) of 0.3 or less, and / or (c) a ratio of ionic strength AO to ionic strength A (ionic strength AO / ionic strength A) of 0.1 or more or 0.2 or more, and / or (d) a 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) of 100 or more, and / or (e) a ratio of ionic strength AO to ionic strength S (ionic strength AO / ionic strength S) of 30 or more, wherein ions s, a, ao, ions b, r, ionic strength S, ionic strength A, ionic strength AO, ionic strength B, and ionic strength R are as follows:

[0013] Ion s is a positive ion with m / z 43.97. Ion a is a positive ion with m / z 43.00, a positive ion with m / z 59.03, and a positive ion with m / z 73.05. Ion ao is a negative ion with m / z 31.02, a negative ion with m / z 59.00, a negative ion with m / z 74.99, a positive ion with m / z 102.97, and a negative ion with m / z 134.96. Ion b is a positive ion with m / z 78.99 and a positive ion with m / z 138.95. Ion r is a positive ion with m / z 29.04 and a positive ion with m / z 55.06.

[0014] Ion intensity S is the intensity of the positive ion at m / z 43.97. Ion intensity A is the sum of the intensities of the positive ions at m / z 43.00, m / z 59.03, and m / z 73.05. Ion intensity AO is the sum of the intensities of the negative ions at m / z 31.02, m / z 59.00, m / z 74.99, m / z 102.97, and m / z 134.96. Ion intensity B is the sum of the intensities of the positive ions at m / z 78.99 and m / z 138.95. Ion intensity R is the sum of the intensities of the positive ions at m / z 29.04 and m / z 55.06.

[0015] In the present invention, ions detected by time-of-flight secondary ion mass spectrometry are identified by m / z (a dimensionless quantity obtained by dividing the mass m of an ion by the valence of the ion). The intensity of an ion (ion intensity) is a value that depends on the number of ions detected by time-of-flight secondary ion mass spectrometry (a value detected for each ion of each m / z).

[0016] The silicon oxide vapor deposition film of the present invention can be produced by a plasma CVD method using a reactive gas containing an organosilicon compound, and it is believed that by leaving a certain proportion of hydroxyl groups and alkoxy groups in the silicon oxide vapor deposition film, the film will exhibit slippage and / or oil repellency for oils and fats or oil-containing compositions.

[0017] The content of components containing hydroxyl groups and / or alkoxy groups and / or alkyl groups in a silicon oxide vapor-deposited film correlates with the intensity of peaks derived from functional groups, which is obtained by analyzing the surface of the silicon oxide vapor-deposited film by time-of-flight secondary ion mass spectrometry (TOF-SIMS). Therefore, the silicon oxide vapor-deposited film of the present invention is required to have a certain ratio of the ionic strength of ions presumed to contain hydroxyl groups and / or alkoxy groups and / or alkyl groups to the ionic strength of ions presumed to be derived only from silicon oxide, as measured by time-of-flight secondary ion mass spectrometry.

[0018] The ions assumed to be derived only from silicon oxide (ion s) are positive ions with m / z 43.97 (SiO), and the ionic strength of this ion is ionic strength S. The ions assumed to contain alkyl groups (ion a) are positive ions with m / z 43.00 (SiCH), positive ions with m / z 59.03 (SiC2H7), and positive ions with m / z 73.05 (SiC3H9), and the sum of these ionic strengths is ionic strength A. The ions assumed to contain alkoxy groups (ions ao) are the negative ions with m / z 31.02 (CH3O), the negative ions with m / z 59.00 (SiCHO), the negative ions with m / z 74.99 (SiCH3O2), the positive ions with m / z 102.97 (Si2CH3O2), and the negative ions with m / z 134.96 (Si2CH3O4), and the sum of these ionic intensities is the ionic strength AO. Furthermore, the ions assumed to contain hydroxyl groups (ions b) are the positive ions with m / z 78.99 (SiO3H3) and the positive ions with m / z 138.95 (SiO5H3), and the sum of these ionic intensities is the ionic strength B. Furthermore, ions assumed to be ions of only hydrocarbons (ions r) are the positive ions of m / z 29.04 (C2H5) and the positive ions of m / z 55.06 (C4H7), and the sum of these ion intensities is the ion intensity R.

[0019] The silicon oxide vapor-deposited film of the present invention is a silicon oxide vapor-deposited film in which, in terms of ionic intensities measured by time-of-flight secondary ion mass spectrometry of the surface of the silicon oxide vapor-deposited film, (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, particularly preferably 150 or more, and particularly preferably 200 or more. The silicon oxide vapor-deposited film of the present invention is preferably a silicon oxide vapor-deposited film in which, in terms of ionic intensities measured by time-of-flight secondary ion mass spectrometry of the surface of the silicon oxide vapor-deposited film, (b) the ratio of ionic strength R to ionic strength A (ionic strength R / ionic strength A) is 0.3 or less, preferably 0.2 or less, and even more preferably less than 0.1. (c) The ratio of ionic strength AO to ionic strength A (ionic strength AO / ionic strength A) is 0.1 or more, preferably 0.1 to 1.0, and more preferably 0.1 to 0.6. In another embodiment, the silicon oxide vapor-deposited film of the present invention is a silicon oxide vapor-deposited film in which, in the ionic strength measurement obtained by time-of-flight secondary ion mass spectrometry of the surface of the silicon oxide vapor-deposited film, the ratio of the sum of ionic strength A and ionic strength AO to (d) 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-deposited film of the present invention is a silicon oxide vapor-deposited film in which, in the ionic strength measurement obtained by time-of-flight secondary ion mass spectrometry of the surface of the silicon oxide vapor-deposited film, the ratio of ionic strength AO to (a)' ionic strength B (ionic strength AO / ionic strength B) 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-deposited film of the present invention, in the ionic strength measurement of the surface of the silicon oxide vapor-deposited film by time-of-flight secondary ion mass spectrometry, the ratio of ionic strength R to ionic strength A (ionic strength R / ionic strength A) may be 0.0 or more or exceed 0.0.The silicon oxide vapor-deposited film of the present invention is a silicon oxide vapor-deposited film in which, in the ionic strengths measured by time-of-flight secondary ion mass spectrometry of the surface of the silicon oxide vapor-deposited film, (c)' the ratio of the ionic strength AO to the ionic strength A (ionic strength AO / ionic strength A) is preferably 1 or less, more preferably 0.6 or less. The silicon oxide vapor-deposited film of the present invention is a silicon oxide vapor-deposited film in which, in the ionic strengths measured by time-of-flight secondary ion mass spectrometry of the surface of the silicon oxide vapor-deposited film, (d)' the ratio of the sum of the ionic strength A and the ionic strength AO to the 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.

[0020] In another embodiment, the silicon oxide vapor-deposited film of the present invention is a silicon oxide vapor-deposited film in which, in the ionic strengths measured by time-of-flight secondary ion mass spectrometry of the surface of the silicon oxide vapor-deposited film, (e) the ratio of ionic strength AO to ionic strength S (ionic strength AO / ionic strength S) may be 30 or more, preferably 40 or more, more preferably 80 or more, even more preferably 100 to 8,000, and particularly preferably 100 to 5,000.

[0021] Furthermore, with regard to the ionic strength, (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, even more preferably 300 or more, and particularly preferably 1000 or more. Here, as for the above conditions (a) to (f) and (a)' to (d)', as long as (a) is satisfied, one or more of the conditions (b) to (f) and (a)' to (d)' may or may not be satisfied in combination.

[0022] In the present invention, time-of-flight secondary ion mass spectrometry can be performed using a commercially available device. For example, a time-of-flight secondary ion mass spectrometer ("TOF.SIMS5" manufactured by ION-TOF GmbH, Germany, measurement area: 500 μm square, primary ion source: Bi) sold by Hitachi High-Tech Science Corporation can be used.

[0023] The silicon oxide vapor-deposited film of the present invention can achieve the sliding property and / or oil repellency of the oil or oil-containing composition by covering the surface, and therefore the thickness of the film is not considered to have any particular effect. The thickness of the film is not particularly limited, but is preferably 1 to 800 nm, more preferably 5 to 500 nm, even more preferably 8 to 400 nm, particularly preferably 10 to 300 nm, and most preferably 10 to 150 nm.

[0024] The thickness of the silicon oxide vapor-deposited film can be measured using, for example, a microscopic film thickness meter (model number: OPTM-A1) manufactured by Otsuka Electronics Co., Ltd., a microscopic automatic film thickness measurement system (model number: F54 XY 200UV) manufactured by Filmetrics Inc., a stylus film thickness meter "DEKTAK" manufactured by Bruker, or by preparing a cross section of the film and measuring it with a field emission scanning electron microscope "JSM-7800F Prime" manufactured by JEOL Ltd. (magnification: 30,000 times, acceleration voltage: 2 kV, working distance: 10.3 mm).

[0025] [Molded Article] The molded article of the present invention is a molded article whose surface is coated with the silicon oxide vapor deposition film described above. The surface coating may be the entire inner or outer surface of the molded article, or a portion thereof, but from the viewpoint of the dischargeability of the contents, it is preferable to mean the coating of the inner surface of the molded article. Note that the aforementioned surface refers to the outermost layer of the molded article. Furthermore, the silicon oxide vapor deposition film of the present invention may have another coating between the substrate of the molded article to be coated and the coating layer of the present invention.

[0026] 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 providing the silicon oxide vapor-deposited film on the surface of the molded article, it is possible to obtain a molded article that is prevented from being soiled with oil and grease and has improved oil removability. Suitable resins include thermoplastic resins known per se, such as low-density polyethylene, high-density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, polyolefins (e.g., 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 (e.g., ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl chloride copolymer), styrene-based resins (e.g., polystyrene, acrylonitrile-styrene copolymer, A copolymer), and the like. Examples of suitable resins include biodegradable resins such as polyethylene terephthalate, polybutylene terephthalate, and polylactic acid, as well as mixtures thereof. Examples of suitable resins include polyethylene and polyethylene terephthalate. Examples of suitable metals include one or more metals selected from iron, nickel, copper, zinc, lead, aluminum, chromium, titanium, and the like, or alloys containing one or more of these metals as a main component. Examples of suitable metals include polyvinyl compounds (e.g., polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinylidene chloride copolymers, polymethyl acrylate, polymethyl methacrylate, and the like), polyamides (e.g., nylon 6, nylon 6-6, nylon 6-10, nylon 11, and nylon 12), thermoplastic polyesters (e.g., polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate), polycarbonate, polyphenylene oxide, and polylactic acid, as well as mixtures thereof. Examples of suitable resins include polyethylene and polyethylene terephthalate. Examples of suitable metals include one or more metals selected from iron, nickel, copper, zinc, lead, aluminum, chromium, and titanium, as well as alloys containing one or more of these metals as a main component. Stainless steel is more preferred.

[0027] These molded articles may be films, sheets, piping, containers, etc., or cooking utensils. Examples of piping include pipes, valves, nozzles, etc. Examples of containers include bottles, tanks, cups, bags, plates, etc., as well as caps and nozzles that constitute containers. Examples of cooking utensils include colanders, nets, stoves, microwave ovens, etc., as well as ventilation fans and cooking tables attached to kitchens. In particular, molded articles such as bottles, tanks, valves, nozzles, etc. for oils and fats are preferred. In addition, the oils and fats are preferably edible. The portion of the molded article coated with the silicon oxide vapor deposition film may be the whole or a part of the molded article, and in particular, it may be only the surface portion that comes into contact with the oils and fats or the oil-containing composition.

[0028] In the molded article of the present invention, the contact angle of refined rapeseed oil at 20°C on the surface covered with the silicon oxide vapor-deposited film is preferably 25° or more, more preferably 30 to 70°, even more preferably 35 to 60°, and most preferably 33 to 55°.

[0029] (Sliding property of oils and fats or oil-containing compositions) In the molded article of the present invention, the sliding property of the oils and fats or oil-containing compositions on the surface covered with the silicon oxide vapor-deposited 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 preferable. For example, the sliding property of the oils and fats or oil-containing compositions can be judged to be better in the following order: more than 60 seconds to 300 seconds, more than 20 seconds to 60 seconds, more than 10 seconds to 20 seconds, and within 10 seconds. Sliding property of oils and fats or oil-containing compositions: the time (seconds) for the rear end of a 24±0.5 mg droplet (or liquid droplet) of oil such as rapeseed oil to move 6 mm on a sample surface inclined at 70° to the vertical at 23±3°C. Here, sliding property may be measured for any product (oil-containing composition) containing oils and fats or oils. In this specification, the term "oil" refers not only to oils that refer to liquid oils and fats, but also to any product containing oils and fats (oil-containing composition). For example, the "oil" in the context of oil repellency may refer not only to oils and fats, but also to the oil repellency of the oil and fat components in an oil-containing composition. The oil repellency of an oil-containing composition such as a dressing may be evaluated by the amount of the oil-containing composition discharged from the container (residual liquid volume). Furthermore, in this specification, "oil," "oil," and "oil-containing composition" may be interpreted interchangeably. Measurement is performed based on the rear end of a droplet (or liquid droplet) of oil or fat such as rapeseed oil, i.e., the highest point of contact between the sample surface and the oil or fat droplet (or liquid droplet) on the inclined sample surface. Rapeseed oil may be dropped onto a sample surface inclined at 70° from the vertical, or it may be dropped onto a horizontally placed sample surface and then measured at a 70° inclination from the vertical. The sample to be measured is a container for storing the oil or fat or oil-containing composition, and may be measured as is, or a smooth portion of the container for storing the oil or fat or oil-containing composition to be measured may be cut out and used as a sample on a flat or approximately flat plate for measurement. A known method can be used to tilt the sample 70° from the vertical, but for example, AS ONE Corporation's "Stage AG85 (Angle Inclined)" or the like may be used.

[0030] The oil or fat dropped onto the sample surface of the container for storing the oil or fat or oil-containing composition is, for example, rapeseed oil. Refined rapeseed oil can be used, including rapeseed oil sold for edible use or rapeseed oil sold as a reagent. Rapeseed oil sold for edible use can be "refined rapeseed oil" or "rapeseed salad oil" as defined in the JAS standard ("Japanese Agricultural Standards for Edible Vegetable Oils," Ministry of Agriculture, Forestry and Fisheries Notification No. 681, August 19, 2019). For example, "Nissin Canola Oil" (manufactured by Nisshin Oillio Group, Inc.) can be used. Furthermore, "rapeseed oil" (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.: Wako Grade 1) can be used as a reagent. To improve the visibility of the rapeseed oil, an oil-soluble colorant can be added. For example, approximately 0.1% by mass of beta-carotene can be added to the rapeseed oil. The addition of this level of beta-carotene does not substantially affect the sliding property of the oil itself (the sliding property of the oil does not substantially change depending on the presence or absence of beta-carotene). Refined rapeseed oil typically contains 51-66% by mass of oleic acid, 19-28% by mass of linoleic acid, 2-11% by mass of linolenic acid, 3-6% by mass of palmitic acid, and 1-3% by mass of stearic acid. The amount of the oil mixture dropped is 24±0.5 mg, preferably about 24.36 mg, which is the amount of one drop from a commercially available dropper. Furthermore, when the oil-containing composition is stored in a container, various compositions containing oils, such as emulsified dressings (including mayonnaise and mayonnaise-type dressings) and separated dressings, may be used instead of the oil, and the sliding property may be measured in the same manner as above.

[0031] [Method for Producing Molded Article] The molded article of the present invention is produced by coating a molded article with a silicon oxide vapor deposition film by a plasma CVD method using an organosilicon compound and any oxidizing gas as reactive gases.

[0032] (Organosilicon Compound and Oxidizing Gas) In the method for producing a molded article of the present invention, an organosilicon compound is used as a silicon source for forming a silicon oxide vapor-deposited film. Examples of the organosilicon compound include organosilane compounds (e.g., hexamethyldisilane, vinyltrimethylsilane, methylsilane, dimethylsilane, tetramethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, methyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane), and organosiloxane compounds (e.g., octamethylcyclotetrasiloxane, 1,1,3,3-tetramethyldisiloxane, and hexamethyldisiloxane), diethoxydimethylsilane, and dimethyldimethoxysilane. 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. Silane (SiH4) or silicon tetrachloride can also be used in combination with the above-mentioned organosilicon compounds. The organosilicon compound preferably has an organic functional group selected from a methyl group, a methoxy group, an ethyl group, and an ethoxy group, more preferably an organosilicon compound having an ethoxy group and / or a methoxy group, and even more preferably an organosilicon compound having only an ethoxy group. Furthermore, an organosilicon compound having only a methyl group is even more preferred. Tetraethoxysilane, tetramethoxysilane, hexamethyldisilazane, hexamethyldisiloxane, etc. are preferred, and an organosilicon compound containing only hexamethyldisiloxane or hexamethyldisiloxane is more preferred. It is preferable that the organosilicon compound does not contain fluorine.

[0033] The oxidizing gas may be oxygen or NOx, with oxygen being preferred. The carrier gas and discharge stabilizing gas may be a rare gas such as argon or helium.

[0034] In the method for producing a molded article of the present invention, a molded article is preferably coated with a silicon oxide vapor-deposited film by a plasma CVD method in which the ratio of the oxidizing gas flow rate (volume) to the total reactant gas flow rate (volume) is 0 to 95% by volume. By using these conditions, a silicon oxide vapor-deposited film can be obtained that exhibits excellent oil- and / or fat-containing properties, particularly with respect to the slipperiness and / or oil-repellency of oils and fats or oil-containing compositions. The ratio of the oxidizing gas flow rate (volume) to the total reactant gas flow rate (volume) is preferably 1 to 65% by volume or 0 to 60% by volume, more preferably 2 to 40% by volume or 0 to 30% by volume, and most preferably 5 to 10% by volume. The flow rate of the reactant gas depends on the surface 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, the reactant gas is preferably supplied at a flow rate of 3 to 2000 sccm, particularly 5 to 600 sccm, per container. The term "sccm" refers to the amount (cc or ml) of gas flowing per minute at 0° C. and 1 atmosphere.

[0035] (Plasma CVD Method) In the present invention, a substrate surface held in a plasma treatment chamber is subjected to plasma treatment by the plasma CVD method in an atmosphere containing the above-mentioned organosilicon compound, an optional oxidizing gas, and, if necessary, a carrier gas, to form a vapor-deposited film having the above-mentioned composition.

[0036] During plasma treatment, the plasma treatment chamber is maintained at a vacuum level sufficient to generate glow discharge, and the pressure during film formation is preferably 1 to 200 Pa, more preferably 3 to 100 Pa. Under this condition, microwaves (300 MHz to 300 GHz) or radio frequency waves (1 to 300 MHz) are supplied to form a silicon oxide vapor deposition film by glow discharge. For example, the microwave output is preferably in the range of 10 to 1000 W, more preferably 20 to 1000 W. The microwave frequency is preferably 500 MHz to 30 GHz, more preferably 1 to 10 GHz. The radio frequency output is preferably 20 to 1500 W, more preferably 30 to 1500 W. The radio frequency frequency is preferably 1 to 100 MHz, more preferably 1 to 30 MHz, and even more preferably 10 to 15 MHz.

[0037] In the method for producing a molded article of the present invention, it is sufficient that the outermost layer of the molded article is a silicon oxide vapor-deposited film coated under the above conditions, and a molded article coated under other conditions may be further coated under the above production conditions. Also, the conditions of the plasma CVD method may be changed, for example by changing the amount of oxidizing gas supplied, and the final coating may be performed under the above production conditions.

[0038] 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 thereto. Furthermore, hereinafter, "%" refers to mass % unless otherwise specified. In the tables, "AO / B" means "ionic strength AO / ionic strength B," "AO / A" means "ionic strength AO / ionic strength A," "(A+AO) / S" means "(ionic strength A+ionic strength AO) / ionic strength S," "AO / S" means "ionic strength AO / ionic strength S," "A / S" means "ionic strength A / ionic strength S," and "R / A" means "ionic strength R / ionic strength A."

[0039] [Analysis Method] (Surface Functional Group Analysis) The surfaces of the silicon oxide vapor-deposited film samples of the Examples and Comparative Examples were analyzed using a time-of-flight secondary ion mass spectrometer ("TOF.SIMS5" sold by Hitachi High-Tech Science Corporation, accelerating voltage: 30 kV, measurement area: 500 μm square, primary ion source: Bi (bismuth)). From the ionic intensities of the obtained peaks, 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 strength A), the ratio of the sum of ionic intensity A and ionic strength AO to ionic strength S ((ionic strength A+ionic strength AO) / ionic strength S), the ratio of ionic intensity AO to ionic strength S (ionic strength AO / ionic strength S), the ratio of ionic intensity A to ionic strength S (ionic strength A / ionic strength S), and the ratio of ionic intensity R to ionic strength A (ionic strength R / ionic strength A) were calculated. Here, the ion intensity (ion intensity) refers to a value (value detected for each m / z ion) that is dependent on the number of ions detected by time-of-flight secondary ion mass spectrometry. Ion intensity S is the intensity of the positive ion of m / z 43.97, ion intensity A is the total value of the intensities of the positive ions of m / z 43.00, the positive ions of m / z 59.03, and the positive ions of m / z 73.05, ion intensity AO is the total value of the intensities of the negative ions of m / z 31.02, the negative ions of m / z 59.00, the negative ions of m / z 74.99, the positive ions of m / z 102.97, and the negative ions of m / z 134.96, and ion intensity B is the total value of the intensities of the positive ions of m / z 78.99 and the positive ions of m / z 138.95. The ion intensity R was the sum of the ion intensities of the positive ion at m / z 29.04 and the positive ion at m / z 55.06.

[0040] (Film Thickness) The film thickness of the silicon oxide vapor-deposited film of each of the Examples and Comparative Examples was measured using a microspectrophotometric film thickness meter (model number: OPTM-A1) manufactured by Otsuka Electronics Co., Ltd. A 20x reflective objective lens was used, and the measurement spot was set to 10 μm.

[0041] (Contact Angle) Measurements were made using a contact angle meter ("DMo-502" manufactured by Kyowa Interface Science Co., Ltd.) with the contact angle meter set to "Contact Angle Measurement [Seasaceous Droplet Method]." The liquid used to measure the contact angle was refined rapeseed oil ("Nissin Canola Oil" manufactured by Nisshin Oillio Group, Inc.), with the amount of liquid used per measurement being 2.0 μL. The oil was supplied to the contact angle meter using a "Teflon (registered trademark) coated needle" (manufactured by Kyowa Interface Science Co., Ltd.). Since oil has a high viscosity and spreads over time after contact with the silicon oxide vapor-deposited film sample surfaces of the Examples and Comparative Examples, the value recorded 50 seconds after contact, when the contact angle had stabilized to a certain extent, was used. Analysis was performed using the θ / 2 method (the radius r and height h of the droplet were determined by image processing, and θ = 2 arctan (h / r) was used for calculation).

[0042] (Oil and fat sliding property) A container for storing oils and fats (PET container: usage capacity 600 g, inner diameter of the upper opening 30.3 mm, height 218.7 mm) was prepared. A 2 cm square PET plate was cut out from the flat portion of the storage container before filling it with oil and fat, and refined rapeseed oil ("Nissin Canola Oil" manufactured by Nisshin Oillio Group Co., Ltd. 99.9%) colored with carotene ("β-Carotene 30% FS" manufactured by DMS 0.1%) was dropped with a dropper (approximately 24.36 mg). The sample was immediately placed on a stage ("Stage (Angle Inclination)" manufactured by AS ONE Corporation) set at an inclination of 70 ° with respect to the vertical direction, and the rear end of the oil and fat droplet (the uppermost contact point between the evaluation sample surface and the oil and fat droplet on the inclined evaluation sample surface) The time it took for the sample surface to move 6 mm was measured. The temperature during measurement was room temperature (23°C). Evaluation was made based on the following criteria A to E according to the transfer time, and if it was A to D, it was determined that the oil sliding property and / or oil repellency effect was present. Here, the shorter the transfer time, the higher the oil sliding property and / or oil repellency effect, and it can be judged that it is good. A rating: 10 seconds or less B rating: More than 10 to 20 seconds C rating: More than 20 to 60 seconds D rating: More than 60 to 300 seconds E rating: More than 300 seconds

[0043] (Reduction rate of residual fat amount) The fat storage containers of the examples and comparative examples were prepared as container samples. When the container sample was a filled PET sample (a container sample obtained by filling rapeseed oil or the like into a polyethylene terephthalate container coated with a silicon oxide vapor deposition film described below and sealing it), the cap was removed to open the top opening of the container, and the container was then quickly tilted at an angle of 160° relative to the vertical to drain the rapeseed oil. When the container sample was a filled pillow sample (a container sample obtained by forming a film sample coated with a silicon oxide vapor deposition film described below into a pillow shape, filling it with rapeseed oil or the like, and sealing it), the heat-sealed portion of the opening was cut to open the top opening of the container, and the container was then quickly tilted at an angle of 180° relative to the vertical to drain the rapeseed oil. The time when the rapeseed oil began to drain from the top opening of the container was defined as 0 seconds, and the tilt was returned to its original position 600 seconds later, and the amount of rapeseed oil remaining in the container (amount of residual fat or oil) was measured. The test was carried out at room temperature (23°C). When the amount of residual oil and fat in the container for storing oils and fats of Comparative Example 1 or Comparative Example 8 was taken as B (mass%) and the amount of residual oil and fat in the container for storing oils and fats of each of the other Examples or Comparative Examples was taken as A (mass%), the reduction rate of the amount of residual oil and fat was calculated using the following formula: Reduction rate of residual oil and fat amount (%) = (1 - A / B) x 100

[0044] (Amount of Residual Liquid in Dressing) The oil and fat storage containers of the Examples and Comparative Examples were prepared as container samples. After mixing by inverting 100 times with the cap still attached, the cap was removed to open the top opening of the container, and the container was quickly tilted at an angle of 160° relative to the vertical to drain the internal solution (filled dressing). The time when the internal solution began to drain from the top opening of the container was set to 0 seconds, and 600 seconds later, the tilt was returned to its original position and the amount of internal solution remaining in the container (amount of residual liquid) was measured. The test was carried out at room temperature (23°C). When the amount of residual liquid in the oil and fat storage container of Comparative Example 1 was set to D (mass%) and the amount of residual liquid in the oil and fat storage containers of each of the other Examples was set to C (mass%), the reduction rate of the residual liquid amount was calculated using the following formula: Reduction rate of residual liquid amount (%) = (1 - C / D) x 100

[0045] [Comparative Examples and Examples] (Plasma CVD Apparatus 1) The film formation conditions using the plasma CVD apparatus 1 used in Comparative Examples 2 to 6 and Examples 1 to 5 are as shown in Table 1. The settings of the plasma CVD apparatus 1 other than those shown in Table 1 are as follows: Name: Plasma CVD apparatus 1 Film formation method: PECVD (Plasma Enhanced Chemical Vapor Deposition) Plasma source: CCP (Capacitively Coupled Plasma) Electrode shape: Similar type (to the container shape) External RF electrode: Upper and lower 2-piece structure, no cooling mechanism Internal gas introduction electrode: φ6.35 mm, no heating mechanism Material: Aluminum alloy (external electrode), SUS304 (internal electrode) RF power supply: Frequency 13.56 MHz RF switch: For 2 channels Matching method: Automatic impedance matching Exhaust configuration: Mechanical booster pump (main pull), rotary pump (auxiliary) Exhaust manifold External dimensions: 350 mm x 350 mm x H150 mm

[0046] (Plasma CVD Apparatus 2) The film formation conditions for the plasma CVD apparatus 2 used in Comparative Example 7 and Examples 6 and 7 are as shown in Table 8. Plasma CVD apparatus 2 had the same settings as the plasma CVD apparatus 1 described above, except that the electrode portions of the plasma CVD apparatus 1 were changed to parallel plate electrodes (electrode distance 50 mm, upper gas shower electrode: made of aluminum alloy and SUS304, heated, φ320 mm, lower RF electrode: made of SUS304, water-cooled, φ320 mm). Note that the first electrode does not also serve as the plasma processing chamber, and the parallel plate first and second electrodes are installed within the plasma processing chamber.

[0047] Experiment 1 (Preparation 1 of Silicon Oxide Vapor Deposition Film and Molded Article) A commercially available uncoated polyethylene terephthalate container for edible oils and fats (PET container: bottle-shaped, usable capacity 600 g, inner diameter of upper opening 30.3 mm, height 218.7 mm, Comparative Example 1) was subjected to plasma treatment using plasma CVD apparatus 1 (details described above) in an organosilicon compound atmosphere under the film-forming conditions shown in Table 1, thereby coating the PET container with a silicon oxide vapor deposition film, and preparing container samples (samples of containers for storing oils and fats) for Comparative Examples 2 to 6 and Examples 1 to 4. Specifically, the container samples for Comparative Examples 2 to 6 and Examples 1 to 4 used tetraethoxysilane (hereinafter sometimes referred to as TEOS), tetramethoxysilane (hereinafter sometimes referred to as TMOS), or hexamethyldisiloxane (hereinafter sometimes referred to as HMDSO) as the organosilicon compound. Oxygen (O) was used as an oxidizing gas mixed with the organosilicon compound as needed and used as a reactive gas. Helium (He) was used as a carrier gas for TEOS, and argon (Ar) was used as a discharge stabilizing gas. The uncoated PET container was first placed in the plasma treatment chamber of the plasma CVD apparatus 1. The pressure in the plasma treatment chamber was reduced to 1 Pa or less, and then the reactive gas and optional carrier gas and discharge stabilizing gas were introduced into the plasma treatment chamber at flow rates shown in Table 1. The pressure was stabilized to the pressure shown in Table 1 over 30 to 60 seconds, and then discharge was performed at the plasma output and for the time shown in Table 1 to coat the surface of the PET container with a silicon oxide vapor deposition film. After discharge, the introduction of the reactive gas and optional carrier gas and discharge stabilizing gas was stopped, the pressure in the deposition chamber was reduced to 1 Pa or less, the plasma treatment chamber was opened to the atmosphere, and the PET container was removed from the plasma treatment chamber.

[0048] The PET container coated with the silicon oxide vapor deposition film described above was filled with 600 g of refined rapeseed oil ("Nissin Canola Oil" manufactured by The Nisshin Oillio Group, Inc.) and sealed to prepare a filled PET sample (container sample). The residual oil amount and the reduction rate of the residual oil amount of the container sample were measured. A 2 cm square PET plate was also cut from the flat surface of the PET container (container sample) coated with the silicon oxide vapor deposition film, and the ionic strength and its ratio, film thickness, contact angle, and oil-slippage property were analyzed and evaluated as described above. The results are shown in Table 2. Furthermore, the container sample was subjected to the following storage test 1 or 2 to measure the reduction rate of the residual oil amount ("Residual Oil Amount" and "Reduced Rate of Residual Oil Amount" in Table 3 (Storage Test 1) and Table 4 (Storage Test 2)). After measuring the reduction rate of the residual oil amount, the container was cut, and the contact angle and oil-slippage property of the portion without oil were measured as described above. The contact angle was measured after washing with hexane and drying. The results are shown in Table 3 (storage test 1) and Table 4 (storage test 2).

[0049] (Storage Test 1: Accelerated Test) Approximately 600 g of refined rapeseed oil ("Nissin Canola Oil" manufactured by The Nisshin Oillio Group, Inc.) was filled into the container samples of Comparative Examples 1 to 6 and Examples 1 to 4, and the containers were sealed with caps. The sealed container samples containing the refined rapeseed oil were stored in a dark place at 60°C for 8 weeks. Note that, because a 10°C increase in temperature accelerates the chemical reaction by approximately two times, the results of the accelerated test at 60°C for 8 weeks described above correspond to the results of storage at room temperature (20°C) for 128 weeks (8 weeks x 16).

[0050] (Storage Test 2: Light Exposure Test) The above-mentioned refined rapeseed oil-containing sealed container samples were stored at 20° C. under light of 1,000 Lux for 6 weeks.

[0051]

[0052]

[0053]

[0054]

[0055] <Experiment 2> (Preparation 2 of silicon oxide vapor-deposited film and molded article) A commercially available uncoated polyethylene terephthalate container for edible fats and oils (PET container: bottle-shaped, usable capacity 600 g, inner diameter of upper opening 30.3 mm, height 218.7 mm, Comparative Example 1) was subjected to plasma treatment using plasma CVD apparatus 1 (details above) under the film-forming conditions in Table 5, in the same manner as in Preparation 1 of silicon oxide vapor-deposited film and molded article, to coat the PET container with a silicon oxide vapor-deposited film, and the container samples (samples of containers for storing fats and oils) of Examples 4 and 5 were prepared. Note that the container samples of Comparative Example 1 and Example 4 were produced under the same conditions as in Experiment 1.

[0056] The PET container (container sample) coated with the silicon oxide vapor deposition film as described above was filled with 600 g of emulsified dressing (commercially available product name "Nissin Dressing Diet Maroyaka Sesame Flavor", manufactured by The Nisshin Oillio Group, Ltd.: 12% by mass of oil (as liquid oil)) or separated dressing (commercially available product name "Nissin Dressing Diet Umakuchi Wafu", manufactured by The Nisshin Oillio Group, Ltd.: 12% by mass of oil (as liquid oil)), and the percentage reduction in the residual liquid volume was measured. The results are shown in Table 6. Furthermore, the following storage test 3 was performed on the same container sample, and the percentage reduction in the residual liquid volume was measured. The results are shown in Table 7 (storage test 3).

[0057] (Storage Test 3: Accelerated Test of Dressing) Approximately 600 g of the above-mentioned emulsified dressing or separated dressing was filled into the container samples of Comparative Example 1, Example 4, and Example 5, and the container was sealed with a cap. The sealed container samples containing the above-mentioned dressing were stored in a dark place at 40°C for 16 weeks.

[0058]

[0059]

[0060]

[0061] Experiment 3 (Preparation 3 of Silicon Oxide Vapor Deposition Film and Molded Article) A commercially available, uncoated, mirror-polished stainless steel plate (#800) (SUS304, 20 mm long, 20 mm wide, 1 mm thick) was subjected to plasma treatment in an organosilicon compound atmosphere under the film-forming conditions shown in Table 8 to coat the stainless steel plate with a silicon oxide vapor deposition film, producing the stainless steel plate samples of Comparative Example 7 and Examples 6 and 7. Specifically, hexamethyldisiloxane (hereinafter sometimes referred to as HMDSO) was used as the organosilicon compound in the stainless steel plate samples of Comparative Example 7 and Examples 6 and 7. Oxygen (O) was mixed with the organosilicon compound as an oxidizing gas as needed and used as a reactive gas. Argon (Ar) was also used as a discharge stabilization gas as needed. First, the uncoated stainless steel plate was placed in the plasma treatment chamber of plasma CVD apparatus 2, and the pressure in the plasma treatment chamber was reduced to 5 Pa or less. The reactive gas and, optionally, a discharge stabilizing gas were then introduced into the plasma treatment chamber at the flow rates shown in Table 8. The pressure was stabilized to the pressure shown in Table 8 over 30 to 60 seconds, and then discharge was carried out at the plasma output and for the time shown in Table 8, thereby coating a silicon oxide vapor-deposited film on the surface of the stainless steel plate. After the discharge, the introduction of the reactive gas and any discharge stabilizing gas was stopped, and the pressure in the film formation chamber was reduced to 5 Pa or less. The plasma treatment chamber was then opened to the atmosphere, and the stainless steel plate was removed from the plasma treatment chamber.

[0062] The ionic strength and ionic ratio, contact angle, and oil-removal properties of the stainless steel plate samples coated with the silicon oxide vapor deposition film as described above were analyzed and evaluated, and the results are shown in Table 9. Furthermore, the stainless steel plate samples were subjected to the following Storage Test 4, and the contact angle and oil-removal properties were measured in the areas where no oil was attached, as described above. The contact angle was measured after washing with hexane and drying. These results are shown in Table 10 (Storage Test 4).

[0063] (Storage Test 4: Heating Test) Approximately 2 kg of refined rapeseed oil ("Nissin Canola Oil" manufactured by The Nisshin Oillio Group, Inc.) was filled into an electric fryer (manufactured by Zojirushi Corporation, product number: EFK-A10) and the oil temperature was adjusted to 180°C. After that, the stainless steel plate samples of Comparative Example 7 and Examples 6 and 7 were placed in the oil and stored for 30 minutes. The stainless steel plate samples were placed so that they would not come into direct contact with the heat source.

[0064]

[0065]

[0066]

[0067] Experiment 4 (Preparation 4 of Silicon Oxide Vapor-Deposited Film and Molded Article) An uncoated polyethylene film (low-density PE film: 120 μm thick) was cut into a 20 cm square, which was designated Comparative Example 8. An evaluation sample treated in the same manner as Comparative Example 8 was subjected to plasma treatment using the plasma CVD apparatus 2 in an organosilicon compound atmosphere under the film-forming conditions listed in Table 11. This resulted in the polyethylene film being coated with a silicon oxide vapor-deposited film, and these were designated the film samples of Examples 8 and 9. Specifically, in the film samples of Examples 8 and 9, hexamethyldisiloxane was used as the organosilicon compound. Oxygen (O) was mixed with the organosilicon compound as an oxidizing gas as needed, and used as the reactive gas. Furthermore, argon (Ar) was used as the discharge stabilization gas as needed. First, the uncoated polyethylene film was placed in the plasma treatment chamber of plasma CVD apparatus 2, and the pressure in the plasma treatment chamber was reduced to 5 Pa or less. The reactive gas and, optionally, a discharge stabilizing gas were then introduced into the plasma treatment chamber at flow rates shown in Table 11. The pressure was stabilized to the pressure shown in Table 11 over 30 to 60 seconds, and then discharge was carried out at the plasma output and for the time shown in Table 11 to coat the surface of the polyethylene film with a silicon oxide vapor deposition film. After the discharge, the introduction of the reactive gas and optional discharge stabilizing gas was stopped, and the pressure in the film formation chamber was reduced to 5 Pa or less. The plasma treatment chamber was then opened to the atmosphere, and the polyethylene film was removed from the plasma treatment chamber.

[0068] The polyethylene film samples coated with the silicon oxide vapor-deposited film as described above were analyzed for ionic strength and ionic ratio. The analysis results are shown in Table 12. Furthermore, the polyethylene film samples were molded into pillow shapes (dimensions: width 10 cm, height 20 cm, opening dimensions: circumference 19 cm), filled with 250 g of refined rapeseed oil ("Nissin Canola Oil" manufactured by The Nisshin Oillio Group, Inc.), and the openings were heat-sealed to produce multiple filled pillow samples. The filled pillow samples were evaluated for the percentage reduction in residual oil and fat content as described below. The evaluation results are shown in Table 12. Furthermore, the filled pillow samples were subjected to the following storage test 5, and the percentage reduction in residual oil and fat content was evaluated as described below. The evaluation results are shown in Table 13.

[0069] (Storage Test 5: Accelerated Test) The filled pillow samples of Comparative Example 8, Example 8 and Example 9 were stored in a dark place at 60° C. for 8 weeks.

[0070]

[0071]

[0072]

Claims

1. A silicon oxide vapor deposition film, wherein the surface of the silicon oxide vapor deposition film has a ratio (ion intensity AO / ion intensity B) of ion intensity AO to ion intensity B of 26 or more in the ion intensity obtained by time-of-flight secondary ion mass spectrometry (wherein ion intensity B is the sum of the intensities of positive ions of m / z 78.99 and positive ions of m / z 138.95; ion intensity AO is the sum of the intensities of negative ions of m / z 31.02, negative ions of m / z 59.00, negative ions of m / z 74.99, positive ions of m / z 102.97, and negative ions of m / z 134.96)).

2. The silicon oxide vapor deposition film according to claim 1, wherein the surface of the silicon oxide vapor deposition film has a ratio (ion intensity R / ion intensity A) of ion intensity R to ion intensity A of 0.3 or less in the ion intensity obtained by time-of-flight secondary ion mass spectrometry (wherein ion intensity A is the sum of the intensities of positive ions of m / z 43.00, positive ions of m / z 59.03, and positive ions of m / z 73.05; ion intensity R is the sum of the intensities of positive ions of m / z 29.04 and positive ions of m / z 55.06).

3. The silicon oxide vapor deposition film according to claim 1 or 2, wherein the surface of the silicon oxide vapor deposition film has a ratio (ion intensity AO / ion intensity A) of ion intensity AO to ion intensity A of 0.1 or more and / or a ratio ((ion intensity A + ion intensity AO) / ion intensity S) of the sum of ion intensity A and ion intensity AO to ion intensity S of 100 or more and / or a ratio (ion intensity AO / ion intensity S) of ion intensity AO to ion intensity S of 30 or more in the ion intensity obtained by time-of-flight secondary ion mass spectrometry (wherein ion intensity S is the intensity of positive ions of m / z 43.97; ion intensity A is the sum of the intensities of positive ions of m / z 43.00, positive ions of m / z 59.03, and positive ions of m / z 73.05).

4. The following grease slipperiness test when rapeseed oil is used as the oil for the silicon oxide vapor deposition film: Grease slipperiness: The rear end of a grease droplet of 24 ± 0.5 mg of rapeseed oil on the surface of a silicon oxide vapor deposition film sample inclined at 70° with respect to the vertical moves 6 mm on the sample surface at 23 ± 3°C in a time (seconds) and has a slipperiness of 300 seconds or less. The silicon oxide vapor deposition film according to any one of claims 1 to 3.

5. The silicon oxide vapor deposition film according to any one of claims 1 to 4, wherein the silicon oxide vapor deposition film is a film derived from hexamethyldisiloxane.

6. A molded article having a surface coated with the silicon oxide vapor deposition film according to any one of claims 1 to 5.

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

8. A method for manufacturing a molded article coated with the silicon oxide vapor deposition film, comprising: (A) a step of preparing a molded article; and (B) a step of coating the surface of the molded article with the silicon oxide vapor deposition film according to any one of claims 1 to 5.

9. The manufacturing method according to claim 8, wherein the coating is performed by a plasma CVD method using an organosilicon compound and an arbitrary oxidizing gas as reaction gases.

10. The manufacturing method according to claim 8 or 9, wherein the silicon oxide vapor deposition film is a film derived from hexamethyldisiloxane.

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