Silicon oxide coating film, molded article, and filled article filled with emulsifier-containing oil / fat composition

Abstract

The present invention provides: a silicon oxide coating film that has good oil repellency and / or good oil release even in an emulsifier-containing oil / fat composition; and a molded article. Specifically, the present invention provides a silicon oxide coating film for use in applications where the coating film comes into contact with an emulsifier-containing oil / fat composition, wherein the surface free energy (γ) of the surface of the silicon oxide coating film at 20°C is 27 mJ / m2 or less.

Description

Silicon oxide coated film, molded product, and filled product containing emulsifier-containing oil composition

[0001] The present invention relates to a silicon dioxide coating film, a molded article, and a filled article filled with an emulsifier-containing oil composition. In particular, the present invention relates to a silicon dioxide coating film that allows for good oil drainage of the emulsifier-containing oil composition, and a molded article coated with the same silicon dioxide coating film.

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

[0003] On the other hand, if containers and cooking utensils have good cleanability after use and good drainage of contents, work efficiency improves and the environmental burden decreases. Therefore, water-repellent and oil-repellent properties are also required as characteristics of the substrate for containers and cooking utensils. For oil repellency, the use of a specific silicon oxide coating film has been proposed (see Patent Document 3). However, the oil repellency is somewhat inferior to emulsifier-containing oil and fat compositions containing emulsifiers, and sufficient research has not been conducted on silicon oxide compound films with good oil repellency for emulsifier-containing oil and fat compositions.

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

[0005] The object of the present invention is to provide a silicon oxide coating film that has good oil repellency and / or good oil drainage, even in an emulsifier-containing oil composition. Furthermore, the object is to provide a molded product that has good oil repellency and / or good oil drainage, even in an emulsifier-containing oil composition. Furthermore, the object is to provide a product that drains oil well when the emulsifier-containing oil composition is removed from a molded product in which the emulsifier-containing oil composition has been filled.

[0006] As a result of diligent research, the inventors of the present invention have found that by adjusting the surface free energy of the silicon oxide coating film applied to the container, good oil repellency and / or good oil drainage performance can be obtained even with an emulsifier-containing oil composition, and have completed the present invention.

[0007] In other words, one aspect of the present invention may relate to the following: [1] A silicon oxide coating film used in contact with an emulsifier-containing oil composition, wherein the surface free energy (γ) of the surface of the silicon oxide coating film at 20°C is 27 mJ / m 2The silicon oxide coating film is as follows: [2] The silicon oxide coating film according to [1], wherein the silicon oxide coating film is a silicon oxide vapor-deposited film. [3] The silicon oxide coating film according to [1] or [2], wherein the surface of the silicon oxide coating film has an ionic intensity of 30 or more, in terms of ionic intensity obtained by time-of-flight secondary ion mass spectrometry, where the ratio of ionic intensity AO to ionic intensity B (ionic intensity AO / ionic intensity B) is 30 or more, and where the ionic intensity B is the sum of the intensities of the positive ions at m / z 78.99 and m / z 138.95, and the ionic 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. [4] A silicon oxide coating film according to any one of [1] to [3] above, wherein the ratio of ionic strength AO to ionic strength A (ionic strength AO / ionic strength A) is 0.05 or more and 0.4 or less, where 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. [5] The silicon oxide coating film according to any one of [1] to [4], wherein the ratio of the sum of ionic strength A and the ionic strength AO to ionic strength S ((ionic strength A + ionic strength AO) / ionic strength S) is 50 or more, and / or the ratio of the ionic strength AO to ionic strength S (ionic strength AO / ionic strength S) is 20 or more, where the ionic strength S is the strength of a positive ion with m / z 43.97, and the 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. [6] The silicon oxide coating film according to any one of [1] to [5], wherein the silicon oxide coating film is a film derived from hexamethyldisiloxane. [7] The silicon oxide coating film according to any one of [1] to [6], wherein the emulsifier-containing oil composition has a surface tension of 32 mN / m or less at 20°C. [8] A molded article whose surface is coated with a silicon oxide coating film according to any of [1] to [7] above, and which is used in applications in which the silicon oxide coating film comes into contact with an emulsifier-containing oil composition.[9] The molded article according to [8], wherein the molded article is a container, pipe or cooking utensil, molded from a material selected from resin, glass, metal, clay, and paper.

[10] A filled article comprising the molded article according to [8] or [9] and an emulsifier-containing oil composition filled into the molded article.

[11] A method for producing the filled article, comprising the steps of coating the molded article with a silicon oxide coating film according to any one of [1] to [7], and filling the coated molded article with an emulsifier-containing oil composition to obtain the filled article.

[0008] According to the present invention, it is possible to provide manufacturing equipment, transport piping, containers, etc., having a silicon oxide coating film that exhibits good oil repellency and / or good oil drainage performance for emulsifier-containing oil compositions. Furthermore, it is expected that manufacturing equipment, transport piping, containers, tableware, etc., coated on the surface with the silicon oxide coating film will exhibit good oil repellency and / or good oil drainage for emulsifier-containing oil compositions, making it easy to remove oily stains and improving the cleanability against oily stains. In addition, it is expected that the container of the present invention will allow the stored emulsifier-containing oil composition to be used to the very end, reducing the amount of oily residue that will remain inside the container, and improving the recyclability of the container.

[0009] The present invention will be described in detail below. In the embodiments of the present invention, A (numerical value) to B (numerical value) means A or greater and B or less. The preferred embodiments and more preferred embodiments exemplified below can be used in appropriate combinations with each other, regardless of expressions such as "preferred" and "more preferred". Furthermore, the numerical ranges are illustrative 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 used, regardless of expressions such as "preferred" and "more preferred". In addition, terms such as "contains" or "includes" may be read as "essentially" or "consists only" as appropriate.

[0010] [Silicon Oxide Coating Film] The silicon oxide coating film of the present invention is a silicon oxide coating film used in contact with an emulsifier-containing oil composition, wherein the surface free energy (hereinafter sometimes denoted as γ) of the surface of the silicon oxide coating film at 20°C is 27 mJ / m2 The following applies:

[0011] (Coating Film) The silicon oxide coating film of the present invention is a silicon oxide film applied to molded products, etc., and its surface has a specific surface free energy. The silicon oxide coating film of the present invention only needs to have a silicon oxide coating film on the surface that comes into contact with the emulsifier-containing oil composition, and may be a single film or a film consisting of multiple layers or compositions, where the outermost layer surface is a silicon oxide coating film. These silicon oxide coating films can be, for example, those coated with a silica coating agent containing an organic compound. Alternatively, a silicon oxide vapor-deposited film can be used, which is formed by plasma treatment by plasma CVD on the surface of a substrate such as a molded product held in a plasma treatment chamber in an atmosphere containing an organosilicon compound, an arbitrary oxidizing gas, and optionally a carrier gas.

[0012] In the case of plasma CVD, organosilicon compounds are used as silicon sources for the formation of silicon oxide vapor-deposited films. Examples of such organosilicon compounds 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, hexamethyldisiloxane), diethoxydimethylsilane, dimethyldimethoxysilane, etc.). In addition to these materials, silazanes such as hexamethyldisilazane and aminosilanes can also be used. These organosilicon compounds can be used individually or in combination of two or more. Furthermore, silane (SiH4) or silicon tetrachloride can be used in combination with the above-mentioned organosilicon compounds. Organosilicon compounds having only functional groups selected from methyl, methoxy, ethyl, and ethoxy groups are preferred; organosilicon compounds having ethoxy and / or methoxy groups are more preferred; and organosilicon compounds having only ethoxy groups are even more preferred. Organosilicon compounds having only methyl groups are also even more preferred. Tetraethoxysilane, tetramethoxysilane, hexamethyldisilazane, hexamethyldisiloxane, etc., are preferred, and organosilicon compounds containing only hexamethyldisiloxane or hexamethyldisiloxane are more preferred.

[0013] Oxygen or NOx is used as the oxidizing gas, with oxygen being preferred. Noble gases such as argon or helium are used as the carrier gas or discharge stabilizing gas.

[0014] The ratio of the flow rate (volume) of the oxidizing gas to the total flow rate (volume) of the reaction gas is, for example, 0 to 95% by volume, preferably 1 to 65% by volume or 1 to 60% by volume, more preferably 2 to 40% by volume or 2 to 30% by volume, and even more preferably 5 to 10% by volume. The flow rate of the reaction gas depends on the coating area of ​​the molded product to be processed, but for example, when coating the inner surface of a plastic container with a capacity of 400 mL to 1.5 L, it is preferable to supply a flow rate of 3 to 2000 sccm per container, particularly 5 to 600 sccm. "Sccm" means the amount of gas (cc or ml) that flows in one minute at 0°C and 1 atmosphere.

[0015] The conditions for plasma treatment are not particularly limited, but for example, in order to maintain a vacuum level at which glow discharge occurs, the pressure during film deposition is preferably 1 to 200 Pa, and more preferably 3 to 100 Pa. In this state, a silicon oxide coating film (silicon oxide vapor deposition film) is formed by glow discharge by supplying microwaves (300 MHz to 300 GHz) or high-frequency waves (1 to 300 MHz). For example, the microwave output is preferably in the range of 10 to 1000 W, and more preferably 20 to 1000 W. The microwave frequency is preferably 500 MHz to 30 GHz, more preferably 1 to 10 GHz, and even more preferably 1 to 5 GHz. The high-frequency output is preferably 20 to 1500 W, and more preferably 30 to 1500 W. The high-frequency frequency is preferably 1 to 100 MHz, more preferably 1 to 30 MHz, and even more preferably 10 to 15 MHz.

[0016] (Surface Free Energy) In this invention, the surface free energy (γ) of the silicon oxide coating film at 20°C is 27 mJ / m 2 The following conditions result in oil repellency towards emulsifier-containing oil compositions, improving oil drainage. In this invention, the surface free energy (γ) is measured using the contact angle and can be calculated based on the theoretical formula Owens-Wendt(). The surface free energy (γ) of the silicon oxide coating film at 20°C is 26 mJ / m 2The following is preferable, 10 to 26 mJ / m 2 is more preferable, 15 to 26 mJ / m 2 is even more preferable, 20 to 26 mJ / m 2 is even more preferable. The surface free energy (γ) at 20°C of the silicon oxide coating film is further 5.0 mJ / m 2 or more, 12.0 mJ / m 2 or more, or 16.0 mJ / m 2 or more may be acceptable, and also 25.0 mJ / m 2 or less, 24.5 mJ / m 2 or less, 24.0 mJ / m 2 or less, 23.5 mJ / m 2 or less, or 23.0 mJ / m 2 or less may be acceptable.

[0017] Also, in the Owens-Wendt theoretical formula, the component (γ h ) based on hydrogen bonding and dipole-dipole interaction on the surface of the silicon oxide coating film at 20°C is 4 mJ / m 2 or less, and an oil-repellent silicon oxide coating film with good oil drainage can be obtained for the emulsifier-containing oil and fat composition. The component (γ h ) based on hydrogen bonding and dipole-dipole interaction is measured using the contact angle and can be calculated based on Owens-Wendt) similar to the surface free energy. The component (γ h ) based on hydrogen bonding and dipole-dipole interaction on the surface of the silicon oxide coating film at 20°C is 5 mJ / m[[ID=​​​​​​​​​​​​​​​​​2 Below, 3.2mJ / m 2 Below, 3.0mJ / m 2 The following, or 2.5 mJ / m 2 The following is also acceptable.

[0018] (Ionic strength obtained by time-of-flight secondary ion mass spectrometry of the surface) In the present invention, it is preferable that the surface of the silicon oxide coating film has an ionic strength obtained by time-of-flight secondary ion mass spectrometry such that (a) the ratio of ionic strength AO to ionic strength B (ionic strength AO / ionic strength B) is 30 or more. The silicon oxide coating film of the present invention is preferably a silicon oxide coating film in which the surface of the silicon oxide coating film has an ionic strength obtained by time-of-flight secondary ion mass spectrometry such that (b) the ratio of ionic strength AO to ionic strength A (ionic strength AO / ionic strength A) is 0.05 or more and 0.4 or less, and / or (c) 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 50 or more, and / or (d) the ratio of ionic strength AO to ionic strength S (ionic strength AO / ionic strength S) is 20 or more. However, ions s, a, ao, b, ionic strengths S, A, AO, and B are as follows:

[0019] 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.

[0020] The ionic strength S is the strength of the positive ion at m / z 43.97. The ionic strength A is the sum of the strengths of the positive ions at m / z 43.00, m / z 59.03, and m / z 73.05. The ionic strength AO is the sum of the strengths of the negative ions at m / z 31.02, m / z 59.00, m / z 74.99, the positive ion at m / z 102.97, and the negative ion at m / z 134.96. The ionic strength B is the sum of the strengths of the positive ions at m / z 78.99 and m / z 138.95.

[0021] In the present invention, the ions detected by the time-of-flight secondary ion mass spectrometry are identified by m / z (the value obtained by dividing the mass m of the ion by the valence of the ion: a dimensionless value). Also, the ion intensity (ionic strength) is a value depending on the number of ions detected by the time-of-flight secondary ion mass spectrometry (the value detected for each ion of each m / z).

[0022] The silicon oxide coating film of the present invention realizes the following, and it is assumed that the oil repellency of the oil containing an emulsifier is good and oil separation occurs. By leaving hydroxyl groups and alkoxy groups in the silicon oxide coating film at a certain ratio, the surface free energy (γ) is 27 mJ / m 2 The content of components containing hydroxyl groups and / or alkoxy groups and / or alkyl groups in the silicon oxide coating film is difficult to measure directly, and it is considered to be correlated with the intensity of the peak derived from the functional group obtained by analyzing the surface of the silicon oxide coating film by time-of-flight secondary ion mass spectrometry (TOF-SIMS).

[0023]

[0024] ​Ions (ions s) assumed to be derived only from silicon oxide are positive ions of m / z 43.97 (SiO), and the ion intensity of these ions is the ion intensity S. Further, ions (ions a) assumed to contain an alkyl group are positive ions of m / z 43.00 (SiCH3), positive ions of m / z 59.03 (SiC2H7), and positive ions of m / z 73.05 (SiC3H9), and the sum of the ion intensities of these ions is the ion intensity A. Also, ions (ions ao) assumed to contain an alkoxy group are negative ions of m / z 31.02 (CH3O), negative ions of m / z 59.00 (SiCH3O), negative ions of m / z 74.99 (SiCH3O2), positive ions of m / z 102.97 (Si2CH3O2), and negative ions of m / z 134.96 (Si2CH3O4), and the sum of the ion intensities of these ions is the ion intensity AO. Furthermore, ions (ions b) assumed to contain a hydroxyl group are positive ions of m / z 78.99 (SiO3H3) and positive ions of m / z 138.95 (Si2O5H3), and the sum of the ion intensities of these ions is the ion intensity B.

[0025] The silicon oxide coating film of the present invention is a silicon oxide coating film in which, in terms of the ionic intensity obtained by time-of-flight secondary ion mass spectrometry of the surface of the silicon oxide coating film, (a) the ratio of ionic intensity AO to ionic intensity B (ionic intensity AO / ionic intensity B) is more preferably 100 to 100,000, even more preferably 250 to 50,000, and even more preferably 500 to 20,000. The silicon oxide coating film of the present invention is preferably a silicon oxide coating film in which, in terms of the ionic intensity obtained by time-of-flight secondary ion mass spectrometry of the surface of the silicon oxide coating film, (b) the ratio of ionic intensity AO to ionic intensity A (ionic intensity AO / ionic intensity A) is more preferably 0.1 to 0.4 or less, and even more preferably 0.12 to 0.37. In another embodiment, the silicon oxide coating film of the present invention is a silicon oxide coating film in which, in terms of the ionic intensity obtained by time-of-flight type secondary ion mass spectrometry of the surface of the silicon oxide coating film, (c) 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 preferably 100 or more, more preferably 300 to 100,000 or 450 to 50,000, and even more preferably 500 to 45,000 or 550 to 42,000.

[0026] In another embodiment, the silicon oxide coating film of the present invention is a silicon oxide coating film in which, in terms of the ionic intensity obtained by time-of-flight type secondary ion mass spectrometry of the surface of the silicon oxide coating film, (d) the ratio of ionic intensity AO to ionic intensity S (ionic intensity AO / ionic intensity S) is more preferably 50 or more, or 100 or more, even more preferably 100 to 10000 or 80 to 50000, and most preferably 150 to 5000.

[0027] Furthermore, in the ionic strength, (e) the ratio of ionic strength A to ionic strength S (ionic strength A / ionic strength S) is preferably 100 or more, more preferably 200 to 100,000, even more preferably 300 to 60,000, and particularly preferably 400 to 40,000. Here, it is preferable that one or more of the above conditions (a) to (e) be satisfied.

[0028] In this invention, time-of-flight secondary ion mass spectrometry can be performed using commercially available equipment. For example, the 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.

[0029] The silicon dioxide coating film of the present invention can achieve oil repellency and / or oil drainage of emulsifier-containing oil compositions by covering the surface, so the film thickness is not considered to have any particular effect. The film thickness is not particularly limited, but is preferably 1 to 800 nm, more preferably 5 to 500 nm, even more preferably 8 to 400 nm, especially preferably 10 to 300 nm, and most preferably 10 to 150 nm.

[0030] (Emulsifier-containing oil and fat composition) In the present invention, the emulsifier-containing oil and fat composition used for contact with a silicon oxide coating film or a molded product coated with a silicon oxide coating film is an oil and fat composition containing an emulsifier. By containing an emulsifier, the interfacial tension of the composition is reduced compared to oil and fat alone, the affinity with the silicon oxide coating film is improved, and the oil repellency and / or oil drainage is worsened. The present invention aims to have an emulsifier-containing oil and fat composition that has good oil repellency and / or oil drainage even if it has poor oil repellency and / or oil drainage, and therefore, the present invention uses an emulsifier-containing oil and fat composition. In the present invention, the surface tension of the emulsifier-containing oil and fat composition at 20°C is preferably 32 mN / m or less, more preferably 10 to 31 mN / m, or 25 to 30.6 mN / m.

[0031] The emulsifier-containing oil and fat composition contains oil and fat. The oil and fat mainly consists of triglycerides and is used as edible oil and fat, industrial oil and fat, or various raw material oils and fats. The oil and fat may also be glycerides including monoglycerides, diglycerides (glycerol mono fatty acid esters), etc., but in that case, in the present invention, monoglycerides and diglycerides are treated as components of the emulsifier described later.

[0032] As for fats and oils, animal and vegetable fats and oils, fats and oils synthesized from glycerin and fatty acids and fractions thereof, transesterified oils, hydrogenated oils, etc., can be used individually or in combination. Examples of animal and vegetable fats and oils include soybean oil, rapeseed oil, high-oleic rapeseed oil, sunflower oil, high-oleic sunflower oil, olive oil, safflower oil, high-oleic safflower oil, corn oil, cottonseed oil, rice oil, sesame oil, perilla oil, linseed oil, peanut oil, grapeseed oil, beef tallow, milk fat, fish oil, coconut oil, palm oil, palm kernel oil, etc. Examples of fats and oils synthesized from glycerin and fatty acids include fats and oils containing linear saturated fatty acids having 6 to 12 carbon atoms, preferably 8 to 10 carbon atoms, such as medium-chain triglycerides (MCTs) having 8 to 10 carbon atoms. Examples of fractionated oils include palm olein, palm superolein, palm stearin, and palm mid-fraction. Examples of transesterified oils include transesterified oils of palm oil or fractionated palm oil with other liquid oils, or transesterified oils of MCT and vegetable oil. Examples of hydrogenated oils include hydrogenated oils of animal and vegetable oils, hydrogenated oils of fractionated animal and vegetable oils, and hydrogenated oils of transesterified oils.

[0033] The oil and fat content is not particularly limited, but the content in the emulsifier-containing oil and fat composition is preferably 20% by mass or more, or 20 to 99.99% by mass, more preferably 48% by mass or more, or 50.0 to 99.9% by mass, and even more preferably 88% by mass or more, or 90.0 to 99.9% by mass, or 95.0 to 99.5% by mass, or 97.0 to 99.5% by mass, when the total amount of the emulsifier-containing oil and fat composition is considered to be 100% by mass.

[0034] Nonionic surfactants, ionic surfactants, etc., can be used as emulsifiers. For food applications, it is preferable to use one or more food-grade emulsifiers such as monoglycerides, diglycerides, organic acid monoglycerides, polyglycerin fatty acid esters, polyglycerin condensed ricinoleic acid esters, sucrose fatty acid esters, polysorbates, propylene glycol fatty acid esters, sorbitan fatty acid esters, sorbitol fatty acid esters, and lecithin.

[0035] The emulsifier content is not particularly limited, but the content in the emulsifier-containing oil composition is preferably 0.01 to 80% by mass, more preferably 0.1 to 50% by mass, and even more preferably 0.1 to 10% by mass, or 0.5 to 5% by mass, or 0.5 to 3% by mass, when the total weight of the emulsifier-containing oil composition is 100% by mass.

[0036] In addition to the above-mentioned components, the emulsifier-containing oil composition may also use raw materials commonly used in emulsifier-containing oil compositions. Specifically, for example, other raw materials such as ethanol, pH adjusters, seasonings, colorants, fragrances, antioxidants, sugars, sugar alcohols, and stabilizers may be used. The amount of these components can be any amount as long as it does not impair the effects of the present invention, but for example, they can be contained in an amount of 10% by mass or less in an emulsifier-containing oil composition (100% by mass), preferably 0 to 3% by mass or more than 0% by mass and 3% by mass or more than 0% by mass and 1% by mass or

[0037] [Molded Article] The molded article of the present invention has its surface coated with the aforementioned silicon oxide coating film, and the silicon oxide coating film is in contact with the emulsifier-containing oil composition. In other words, the coated molded article of the present invention includes a molded article substrate and the silicon oxide coating film coated on the surface of the molded article substrate. The surface coating may be all or part of the inner and outer surfaces of the molded article, but from the perspective of the discharge of contents, it is preferable that the inner surface of the molded article is coated. The aforementioned surface refers to the outermost layer of the molded article. Furthermore, the silicon oxide coating film of the present invention may have other coatings between the coated molded article substrate and the coating layer according to the present invention.

[0038] The molded article (substrate) of the present invention is preferably molded from a material selected from the group consisting of resin, glass, metal, and paper. By having the aforementioned silicon oxide coating film on the surface of the molded article, a molded article can be obtained that is provided with oil stain prevention and improved oil removal. Suitable resins include thermoplastic resins that are known themselves, such as low-density polyethylene, high-density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, polyolefins (for example, polyolefins such as random or block copolymers of α-olefins such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene), ethylene-vinyl compound copolymers (for example, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl chloride copolymer, etc.), styrene-based resins (for example, polystyrene, acrylonitrile-styrene copolymer, A Examples of resins include biodegradable resins such as BS, α-methylstyrene / styrene copolymer, polyvinyl compounds (e.g., polyvinyl chloride, polyvinylidene chloride, vinyl chloride / vinylidene chloride copolymer, methyl polyacrylate, polymethyl methacrylate, etc.), polyamides (e.g., nylon 6, nylon 6-6, nylon 6-10, nylon 11, nylon 12, etc.), thermoplastic polyesters (e.g., polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polycarbonate, polyphenylene oxide, polylactic acid, or mixtures thereof. More preferably, the resin is polyethylene, polyethylene terephthalate, etc. As for the metal, one or more metals selected from iron, nickel, copper, zinc, lead, aluminum, chromium, titanium, etc., or alloys containing one or more of these metals as main components are preferred, and stainless steel is more preferred.

[0039] These molded products may be films, sheets, pipes, containers, etc., or they may be tableware, cooking utensils, and manufacturing equipment. Examples of pipes include tubes, valves, and nozzles. Examples of containers include bottles, tanks, cups, plastic wrap, bags, plates, etc., as well as caps, nozzles, etc., that make up the containers. Examples of tableware other than containers include chopsticks, spoons, forks, and knives. Examples of cooking utensils include strainers, meshes, stoves, microwave ovens, etc., as well as ventilation fans and countertops attached to kitchens. Examples of manufacturing equipment include food processing machinery, manufacturing equipment for components such as plastic injection molding machines and semiconductor component manufacturing equipment, and manufacturing equipment for chemicals and pharmaceuticals. In particular, it is preferable that the molded products be bottles, tanks, valves, nozzles, etc., for oils and fats. Furthermore, it is preferable that the oils and fats are edible. The portion of the molded product to be coated with the silicon dioxide coating film may be all or part of the molded product, and in particular, it may be just the surface portion that comes into contact with the emulsifier-containing oil composition.

[0040] [Filled Product] The filled product of the present invention is a molded product coated with the aforementioned silicon oxide coating film, filled with the aforementioned emulsifier-containing oil and fat composition. In other words, the filled product includes the coated molded product and the emulsifier-containing oil and fat composition filled into the molded product. An example of the filled product is a molded product (container) made of resin, glass, or metal coated with a silicon oxide coating film, filled with an emulsifier-containing oil and fat composition for food use.

[0041] [Method for Manufacturing Filled Products] The method for manufacturing filled products of the present invention includes the step of filling a molded product coated with the aforementioned silicon oxide coating film with the aforementioned emulsifier-containing oil and fat composition. More specifically, the above manufacturing method includes the steps of coating a molded product (substrate) with a silicon oxide coating film, and filling the coated molded product with an emulsifier-containing oil and fat composition to obtain a filled product. For example, a molded product (container) made of resin, glass, or metal coated with a silicon oxide coating film is filled with an emulsifier-containing oil and fat composition for food use. This makes it possible to obtain a filled product with good oil repellency and / or oil drainage.

[0042] Next, the present invention will be described in more detail with reference to examples, comparative examples, and reference examples, but the present invention is not limited in any way to these. Also, in the following, "%" refers to mass percent unless otherwise specified. In the table, "(A + AO) / S" means "(ionic strength A + ionic strength AO) / ionic strength S", "A / S" means "ionic strength A / ionic strength S", "AO / S" means "ionic strength AO / ionic strength S", "AO / A" means "ionic strength AO / A", and "AO / B" means "ionic strength AO / B".

[0043] [Analysis] (Surface Functional Group Analysis) The internal surface of the oil composition storage containers of the examples and comparative examples was analyzed using a time-of-flight secondary ion mass spectrometer ("TOF.SIMS5", sold by Hitachi High-Tech Science Corporation, acceleration voltage 30kV, measurement area: 500μm square, primary ion source: Bi (bismuth)). From the ionic intensities of the obtained peaks, the ratio of the sum of ionic intensities A and AO to ionic intensity S ((ionic intensity A + ionic intensity AO) / ionic intensity S), the ratio of ionic intensity A to ionic intensity S (ionic intensity A / ionic intensity S), the ratio of ionic intensity AO to ionic intensity S (ionic intensity AO / ionic intensity S), the ratio of ionic intensity AO to ionic intensity A (ionic intensity AO / ionic intensity A), and the ratio of ionic intensity AO to ionic intensity B (ionic intensity AO / ionic intensity B) were calculated. The ion intensity (ionic intensity) referred to here 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 at each m / z). Ionic intensity S is defined as the intensity of the positive ion at m / z 43.97, ionic intensity A is defined as the sum of the intensities of the positive ions at m / z 43.00, m / z 59.03, and m / z 73.05, ionic intensity AO is defined as 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, and ionic intensity B is defined as the sum of the intensities of the positive ions at m / z 78.99 and m / z 138.95.

[0044] (Surface Free Energy) Surface free energy was measured using a contact angle meter ("DMo-502", manufactured by Kyowa Interface Science Co., Ltd.) with the "Surface Free Energy Analysis [Component Calculation B]" setting on the contact angle meter. The liquids used for measuring the contact angle were pure water and diiodomethane (CAS RN: 75-11-6), with a liquid volume of 2.0 μL used for each measurement. The value was recorded 1 second after liquid contact. The temperature during measurement was room temperature (20°C). The θ / 2 method was used for the contact angle analysis (the radius r and height h of the droplet were determined by image processing, and θ was calculated as θ = 2arctan(h / r)). The surface free energy was determined from the contact angles of pure water and diiodomethane. The theoretical formula used to calculate the surface free energy (γ) was "Owens-Wendt". Note that the dispersion component (γ) of pure water was also used. d ) is 21.8 mJ / m 2 , components based on hydrogen bonding and dipole-dipole interactions (γ h ) is 51.0 mJ / m 2 The surface free energy (γ) is 72.8 mJ / m 2 The value of was used. Also, the dispersion component of diiodomethane (γ d ) is 49.5 mJ / m 2 , components based on hydrogen bonding and dipole-dipole interactions (γ h ) is 1.3 mJ / m 2 The surface free energy (γ) is 50.8 mJ / m 2 The value of was used. Note that the variance component (γ) in the table d ), components based on hydrogen bonding and dipole-dipole interactions (γ h The units of surface free energy (γ) are "mJ / m 2 "

[0045] (Surface Tension of Oils and Fats) The surface tension of oils and fats was measured using a contact angle meter. A contact angle meter ("DMo-502," manufactured by Kyowa Interface Science Co., Ltd.) was used, and measurements were taken using the "Interface Tension Measurement [Suspended Drop Method]" setting on the contact angle meter. The amount of liquid used for each measurement was 5.0 μL. For oil supply to the contact angle meter, a "Teflon® coated needle" (manufactured by Kyowa Interface Science Co., Ltd.) was used. The value was recorded 1 second after droplet formation. The temperature during measurement was room temperature (20°C). The Young-Laplace method was used for analysis.

[0046] [Sample] (Uncoated sample) A commercially available polyethylene terephthalate container for edible oils and fats (PET container: usable capacity 600g, inner diameter of the opening at the top 30.3mm, height 218.7mm) that was not coated was cut into a rectangle measuring 30mm in length and 10mm in width to obtain the uncoated sample.

[0047] (Vaporized film samples 1-4) Commercially available polyethylene terephthalate containers for edible oils and fats (PET containers: usable capacity 600g, inner diameter of the opening at the top 30.3mm, height 218.7mm) that were not coated were subjected to plasma treatment using a plasma CVD apparatus (details below) with organosilicon compounds (HMDSO) as raw materials under the film formation conditions shown in Table 1, thereby coating the PET containers with a silicon oxide vapor-deposited film, which became vapor-deposited film samples 1-4 of Comparative Example 2 and Examples 1-3. Specifically, hexamethyldisiloxane (HMDSO) was used as the organosilicon compound. Oxygen (O2) was mixed with the organosilicon compound as an oxidizing gas as needed and used as a reaction gas. In addition, argon (Ar) was used as a carrier gas and discharge stabilizing gas in vapor-deposited film sample 2. First, the PET container was placed in the plasma processing chamber of the plasma CVD apparatus. After reducing the pressure in the plasma processing chamber to 1 Pa or less, the reaction gas and optionally argon gas were introduced into the plasma processing chamber at the flow rates shown in Table 1. The pressure was stabilized to the levels shown in Table 1 over 30 to 60 seconds. Then, a silicon oxide vapor deposition film was coated onto the surface of the PET container by discharging at the plasma output and time shown in Table 1. After the discharge, the introduction of the reaction gas, optional carrier gas, and discharge stabilizing gas was stopped, and the pressure in the deposition chamber was reduced to 1 Pa or less. The plasma processing chamber was then opened to the atmosphere, and the PET container was removed from the plasma processing chamber. It was then cut into rectangles measuring 30 mm in length and 10 mm in width to obtain vapor deposition film samples 1 to 4. Surface functional group analysis was performed on vapor deposition film samples 1 to 4, and the results are shown in Table 2.

[0048] <Plasma CVD System> The conditions for film deposition of samples 1 to 4 are as shown in Table 1. The settings for the plasma CVD system other than those shown in Table 1 are as follows: Name: Plasma CVD system Film deposition method: PECVD (Plasma Enhanced Chemical Vapor Deposition) Plasma source: CCP (Capacitively Coupled Plasma) Electrode shape: Similar type (relative to the container shape) External RF electrode: Upper and lower 2-piece structure, no cooling mechanism Internal gas introduction electrode: φ6.35mm, no heating mechanism Material: Aluminum alloy (external electrode), SUS304 (internal electrode) RF power supply: Frequency 13.56MHz RF switch: 2ch Matching method: Automatic impedance matching Exhaust configuration: Mechanical booster pump (main), rotary pump (auxiliary) Exhaust manifold External dimensions: 350mm x 350mm x H150mm

[0049]

[0050]

[0051]

[0052] (Oils and Fats) Oil 1 (refined rapeseed oil: product name "Nisshin Canola Oil", manufactured by Nisshin Oillio Group Ltd.) was mixed with 1% of an emulsifier (polyglycerin fatty acid ester: product name "Sunsoft A-173E", manufactured by Taiyo Kagaku Co., Ltd.) to create Oil 2. The surface tensions of Oil 1 and Oil 2 at 20°C were as follows: Oil 1: 32.7 mN / m Oil 2: 30.2 mN / m

[0053] [Slipperiness (Oil Drainage)] Undeposited film samples and deposited film samples 1-4 were immersed horizontally in oil up to 2-5 mm below the top edge of the sample, then removed from the oil and held vertically. Within 90 seconds after removal from the oil, the distance traveled by the upper edge of the oil on the vertical centerline of the sample surface (the uppermost contact point between the sample surface and the oil on the sample surface) was measured. The temperature during measurement was room temperature (23°C). A longer distance indicates higher oil slipperiness. Furthermore, since this slipperiness measures the change in the position of the upper edge of the oil, it correlates with oil drainage, and a longer value (distance) indicates better oil drainage. The results are shown in Table 4.

[0054]

[0055] As shown in Table 4, even with the vapor-deposited film sample 1, if the oil 1 does not contain an emulsifier as shown in Reference Example 1, it has sufficient sliding properties. However, the oil 2 containing an emulsifier, while better than Comparative Example 1, has inferior sliding properties. Nevertheless, the surface free energy (γ) is 27 mJ / m 2 It can be seen that using the vapor-deposited film samples 2 to 4 below, the slipperiness (oil drainage) is improved even in oil 2 containing an emulsifier.

Claims

1. A silicon dioxide coating film used in applications involving contact with an emulsifier-containing oil composition, wherein the surface free energy (γ) of the surface of the silicon dioxide coating film at 20°C is 27 mJ / m². 2 The following is a silicon dioxide coating film.

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

3. The silicon oxide coating film according to claim 1 or 2, wherein the surface of the silicon oxide coating film has an ionic intensity of 30 or more, in terms of the ionic intensity obtained by time-of-flight secondary ion mass spectrometry, where the ratio of ionic intensity AO to ionic intensity B (ionic intensity AO / ionic intensity B), and where ionic intensity B is the sum of the intensities of the positive ions at m / z 78.99 and m / z 138.95, and ionic 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.

4. The silicon oxide coating film according to any one of claims 1 to 3, wherein the ratio of ionic strength AO to ionic strength A (ionic strength AO / ionic strength A) is 0.05 or more and 0.4 or less, where 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.

5. The silicon oxide coating film according to any one of claims 1 to 4, wherein 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 50 or more, and / or the ratio of ionic strength AO to ionic strength S (ionic strength AO / ionic strength S) is 20 or more, where ionic strength S is the strength of a positive ion with m / z 43.97, and 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.

6. The silicon dioxide coating film according to any one of claims 1 to 5, wherein the silicon dioxide coating film is a film derived from hexamethyldisiloxane.

7. The silicon dioxide coating film according to any one of claims 1 to 6, wherein the emulsifier-containing oil composition has a surface tension of 32 mN / m or less at 20°C.

8. A molded article whose surface is coated with a silicon oxide coating film according to any one of claims 1 to 7, and which is used in applications in which the silicon oxide coating film comes into contact with an emulsifier-containing oil composition.

9. The molded article according to claim 8, wherein the molded article is a container, pipe, or cooking utensil, formed from a material selected from resin, glass, metal, clay, and paper.

10. A filled product comprising a molded article according to claim 8 or 9 and an emulsifier-containing oil composition filled into the molded article.

11. A method for producing a filled product, comprising the steps of: coating a molded product with a silicon oxide coating film according to any one of claims 1 to 7; and filling the coated molded product with an emulsifier-containing oil composition to obtain a filled product.

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