Silicon oxide vapor-deposited film, molded article, method for manufacturing a molded article

Abstract

To provide a silicon oxide vapor-deposited film having a high oil-repellent function; a molding coated with the silicon oxide vapor-deposited film having a high oil-repellent function; and a method for manufacturing the same.SOLUTION: In an ion intensity obtained by time-of-flight type secondary ion mass spectrometry on the surface of a silicon oxide vapor-deposited film, the ratio of the total of an ion intensity A and an ion intensity AO to an ion intensity S is 10 or more, and / or the ratio of the ion intensity AO to the ion intensity S is 0.7 or more, (where, the ion intensity S is a positive ion intensity of m / z43.97; the ion intensity A is the total ion intensity of a positive ion of m / z43.00, a positive ion of m / z59.03 and a positive ion of m / z73.05; and the ion intensity AO is the total ion intensity of a negative ion of m / z31.02, a negative ion of m / z59.00, a negative ion of m / z74.99, a positive ion of m / z102.97 and a negative ion of m / z134.96.).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a silicon oxide vapor deposition film having high oil repellency, a molded product coated with the silicon oxide vapor deposition film, and a method for producing a molded product coated with the silicon oxide vapor deposition film.

Background Art

[0002] Conventionally, in order to improve the properties of various substrates, a film is formed on the surface. For example, in packaging materials, it is known to form a vapor deposition film by the plasma CVD method on the surface of a plastic molded product to improve the gas barrier property.

[0003] For example, at least an organosilicon compound and a gas having oxygen or oxidizing power are used, and a silicon oxide and a compound containing at least one or two or more elements selected from carbon, hydrogen, silicon, and oxygen are formed on at least one side of a plastic container by the plasma CVD method. A method for producing a plastic container is known in which the concentration of the organosilicon compound changes when forming a barrier layer (vapor deposition film). The flow rate ratio of the gases of the organosilicon compound (hexamethyldisiloxane) and oxygen was 1:2, 1:20, 1:100 (see Patent Document 1).

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

[0005] On the other hand, if containers and cooking utensils are easy to clean after use and allow for easy 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. As for water repellency, for example, a bottle with good drainage properties 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 mainly composed of silicon oxide compounds is formed on its surface by the CVD method (gas flow rate ratio of hexamethyldisiloxane to oxygen of 1:4). (See Patent Document 3). However, sufficient research had not been conducted on silicon oxide compound films with good oil-repellent properties. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2000-255579 [Patent Document 2] Japanese Patent Publication No. 2003-53873 [Patent Document 3] Japanese Patent Publication No. 2009-46162 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] The object of the present invention is to provide a silicon oxide vapor-deposited film with high oil-repellent properties, a molded article coated with a silicon oxide vapor-deposited film with high oil-repellent properties, and a method for manufacturing a molded article coated with a silicon oxide vapor-deposited film with high oil-repellent properties. [Means for solving the problem]

[0008] As a result of diligent research, the inventors of the present invention discovered that high oil repellency can be obtained by using a silicon oxide vapor-deposited film containing a certain amount of alkyl and / or alkoxy groups, and thus completed the present invention.

[0009] In other words, the present invention provides the following [1] to [9]. [1] The surface of the silicon oxide vapor-deposited film has an ionic intensity of 10 or more, obtained by time-of-flight secondary ion mass spectrometry, where 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 10 or more, and / or the ratio of ionic intensity AO to ionic intensity S (ionic intensity AO / ionic intensity S) is 0.7 or more. Silicon oxide vapor-deposited film. (however, The ionic intensity S is the intensity of the positive ion with m / z 43.97. Ionic 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. 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. [2] The silicon oxide vapor-deposited film of [1], wherein the ratio of the ionic strength AO to the ionic strength A (ionic strength AO / ionic strength A) is 0.2 or more. [3] A molded article whose surface is coated with a silicon oxide vapor-deposited film of [1] or [2]. [4] A molded article of [3], which is made of a material selected from resin, glass, or metal, and is a container, pipe, or cooking utensil. [5] A molded article according to [3] or [4], wherein the contact angle of refined rapeseed oil at 20°C on the surface of the molded article covered with a silicon dioxide vapor-deposited film is 20° or more. [6] A plasma CVD method using an organosilicon compound and an oxidizing gas as the reaction gas is used to coat the molded product with a silicon oxide vapor-deposited film. The surface of the obtained silicon oxide vapor-deposited film has an ionic intensity of 10 or greater, as determined by time-of-flight secondary ion mass spectrometry, where 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 10 or greater, and / or the ratio of ionic intensity AO to ionic intensity S (ionic intensity AO / ionic intensity S) is 0.7 or greater. A method for manufacturing molded products coated with a silicon oxide vapor-deposited film that has high oil repellency. (however, The ionic intensity S is the intensity of the positive ion with m / z 43.97. Ionic 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. 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. [7] A method for manufacturing the molded article according to [6], wherein the ratio of the ionic strength AO to the ionic strength A (ionic strength AO / ionic strength A) is 0.2 or more. [8] A method for manufacturing a molded article according to [6] or [7], wherein the molded article is coated with a silicon oxide vapor deposition film by a plasma CVD method in which the ratio of the flow rate (volume) of the oxidizing gas to the total flow rate (volume) of the reaction gas is 0 to 65 volume%. [9] A method for producing a molded article according to any one of [6] to [8], wherein the organosilicon compound is an organosilicon compound having an ethoxy group and / or a methoxy group as an organic functional group containing carbon, and the oxidizing gas is oxygen. [Effects of the Invention]

[0010] The present invention provides a silicon oxide vapor-deposited film with excellent oil-repellent properties. Furthermore, molded products coated with the silicon oxide vapor-deposited film have good cleanability against oil stains, as oil stains are easily removed. In addition, when the molded product is a container, pipe, etc., it drains oil well and is less likely to leave oil residue. [Modes for carrying out the invention]

[0011] Hereinafter, the present invention will be described in detail with examples. In the embodiments of the present invention, A (numerical value) to B (numerical value) means A or more and B or less. In addition, the preferred embodiments and more preferred embodiments exemplified below can be used in appropriate combinations with each other regardless of the expressions such as "preferred" and "more preferred". In addition, the description of the numerical range is for illustration, and ranges obtained by appropriately combining the upper and lower limits of each range and the numerical values of the examples can also be preferably used regardless of the expressions such as "preferred" and "more preferred". Furthermore, terms such as "containing" or "including" may be read as "essentially consisting of" or "consisting only of" as appropriate.

[0012] [Silicon Oxide Deposition Film] In the silicon oxide deposition film of the present invention, on the surface of the silicon oxide deposition film, in terms of the ion intensity obtained by time-of-flight secondary ion mass spectrometry, the ratio of the sum of the intensity of ion a (ion intensity A) and the intensity of ion ao (ion intensity AO) to the intensity of ion s (ion intensity S) ((ion intensity A + ion intensity AO) / ion intensity S) is 10 or more, and / or the ratio of the intensity of ion ao (ion intensity AO) to the intensity of ion s (ion intensity S) (ion intensity AO / ion intensity S) is 0.7 or more. However, ion s, ion a, ion ao, ion intensity S, ion intensity A, and ion intensity AO are as follows. 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 intensity S is the intensity of the positive ion with m / z 43.97. Ion intensity A is the sum of the intensities of each of the positive ions with m / z 43.00, the positive ion with m / z 59.03, and the positive ion with m / z 73.05. The ionic strength AO is the sum of the intensities of the following ions: the negative ion with m / z 31.02, the negative ion with m / z 59.00, the negative ion with m / z 74.99, the positive ion with m / z 102.97, and the negative ion with m / z 134.96.

[0013] In the present invention, the ions detected by 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 that depends on the number of ions detected by time-of-flight secondary ion mass spectrometry (the value detected for each ion with each m / z).

[0014] The silicon oxide deposition film of the present invention can be manufactured by plasma CVD using a reactive gas containing an organosilicon compound. It is assumed that oil repellency is exhibited by leaving a certain amount or more of an alkyl group and / or an alkoxy group in the silicon oxide deposition film.

[0015] [[ID= (12)]]Since the content of the alkyl group and / or alkoxy group in the silicon oxide deposition film is correlated with the intensity of the peak derived from the functional group obtained by analyzing the surface of the silicon oxide deposition film by time-of-flight secondary ion mass spectrometry (TOF-SIMS), in the silicon oxide deposition film of the present invention, it is essential that the ionic strength of the ion assumed to be based on the alkyl group and / or alkoxy group relative to the ionic strength of the ion assumed to be based on silicon oxide in time-of-flight secondary ion mass spectrometry is a certain value or more.

[0016] The ion assumed to be based on silicon dioxide (ion s) is a positive ion with m / z 43.97 (SiO) and its ionic strength is ionic strength S. The ions assumed to be based on alkyl groups (ion a) are positive ions with m / z 43.00 (SiCH3), m / z 59.03 (SiC2H7), and m / z 73.05 (SiC3H9) and their ionic strengths are summed to form ionic strength A. Furthermore, the ions assumed to be based on the alkoxy group (ion ao) are the negative ion at m / z 31.02 (CH3O), the negative ion at m / z 59.00 (SiCH3O), the negative ion at m / z 74.99 (SiCH3O2), the positive ion at m / z 102.97 (Si2CH3O2), and the negative ion at m / z 134.96 (Si2CH3O4). The sum of these ionic intensities is the ionic strength AO.

[0017] In the silicon oxide vapor-deposited film of the present invention, the ratio of the sum of ionic strengths A and ionic strengths AO to ionic strength S ((ionic strength A + ionic strength AO) / ionic strength S) on the surface of the silicon oxide vapor-deposited film, as obtained by time-of-flight secondary ion mass spectrometry, is preferably 20 or more, more preferably 30 or more, and even more preferably 33 or more. Furthermore, in the silicon oxide vapor-deposited film of the present invention, the ratio of the sum of ionic strengths A and ionic strengths AO to ionic strength S ((ionic strength A + ionic strength AO) / ionic strength S) on the surface of the silicon oxide vapor-deposited film, as obtained by time-of-flight secondary ion mass spectrometry, is preferably 100 or less, more preferably 600 or less, even more preferably 100 or less, and most preferably 80 or less.

[0018] Furthermore, in the silicon oxide vapor-deposited film of the present invention, the ratio of ionic intensity AO to ionic intensity S (ionic intensity AO / ionic intensity S) on the surface of the silicon oxide vapor-deposited film, as obtained by time-of-flight secondary ion mass spectrometry, may be 0.7 or higher, preferably 1 to 200, more preferably 10 to 150, and most preferably 20 to 50.

[0019] Furthermore, in the ionic strength, it is preferable that the ratio of ionic strength A to ionic strength S (ionic strength A / ionic strength S) is 8 or more.

[0020] In the oil-repellent effect of alkyl and alkoxy groups in silicon oxide vapor-deposited films, a higher oil-repellent effect is achieved when there are more alkoxy groups than alkyl groups. Therefore, at the aforementioned peak, the ratio of ionic intensity AO to ionic intensity A (ionic intensity AO / ionic intensity A) is preferably 0.2 or higher, more preferably 0.5 or higher, and even more preferably 1 or higher.

[0021] 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.

[0022] The silicon oxide vapor-deposited film of the present invention achieves oil repellency by covering the surface, so the film thickness is not considered to have any particular effect. The film thickness is not particularly limited, but 1 to 800 nm is preferred, 5 to 500 nm is more preferred, 10 to 400 nm is even more preferred, 30 to 300 nm is particularly preferred, and 80 to 150 nm is most preferred.

[0023] The thickness of the silicon oxide vapor-deposited film can be measured, for example, using a microscopic automated film thickness measurement system (model number: F54 XY 200UV) manufactured by Filmetrics Inc., a stylus-type film thickness gauge "DEKTAK" manufactured by Bruker, or by creating a cross-section of the film and measuring it with an electrolytic emission operating electromicroscope "JSM-7800F Prime" manufactured by JEOL Ltd. (magnification 30,000x, acceleration voltage 2kV, working distance 10.3mm).

[0024] [Molded products] The molded article of the present invention is a molded article whose surface is coated with the aforementioned silicon oxide vapor-deposited film. The surface coating may cover all or part of the molded article. The aforementioned surface refers to the outermost layer of the molded article. In addition, there may be other coatings between the silicon oxide vapor-deposited film of the present invention and the base of the molded article to which it is coated.

[0025] The molded article of the present invention is preferably made from a material selected from resin, glass, or metal. By having the aforementioned silicon oxide vapor-deposited film on the surface of the molded article, it is possible to obtain a molded article that prevents oil stains and improves oil removal. Suitable resins include thermoplastic resins known on their own, such as polyolefins like low-density polyethylene, high-density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, or random or block copolymers of α-olefins such as ethylene, pyropylene, 1-butene, and 4-methyl-1-pentene; ethylene-vinyl compound copolymers such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, and ethylene-vinyl chloride copolymer; styrene-based resins such as polystyrene, acrylonitrile-styrene copolymer, ABS, and α-methylstyrene-styrene copolymer; polyvinyl compounds such as polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinylidene chloride copolymer, methyl polyacrylate, and polymethyl methacrylate; polyamides such as nylon 6, nylon 6-6, nylon 6-10, nylon 11, and nylon 12; thermoplastic polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polycarbonate, polyphenylene oxide, and biodegradable resins such as polylactic acid, or mixtures thereof. Furthermore, as the metal, one metal selected from iron, nickel, copper, zinc, lead, aluminum, chromium, titanium, etc., or an alloy containing one or more of these metals as the main component is preferred, with stainless steel being more preferred.

[0026] These molded products may be films, sheets, pipes, containers, etc., or cooking utensils. Examples of pipes include tubes, valves, nozzles, etc. Examples of containers include bottles, tanks, cups, plates, etc., as well as caps, nozzles, etc. Examples of cooking utensils include strainers, mesh, stoves, microwave ovens, etc., as well as ventilation fans and countertops attached to kitchens. In particular, molded products such as bottles, tanks, valves, and nozzles for oils and fats are preferred. Furthermore, it is preferable that the oils and fats are edible. The portion of the molded product coated with a silicon oxide vapor deposition film may be the whole product or a part of the molded product, and in particular, it may be just the surface portion that comes into contact with the oil.

[0027] In the molded article of the present invention, the contact angle of refined rapeseed oil at 20°C on the surface covered with the aforementioned silicon oxide vapor-deposited film is preferably 20° or more, more preferably 20 to 90°, even more preferably 25 to 80°, and most preferably 30 to 60°.

[0028] [Manufacturing method for molded products] The present invention provides a method for manufacturing molded articles, in which a molded article is coated with a silicon oxide vapor-deposited film by a plasma CVD method using an organosilicon compound and an oxidizing gas as reaction gases, and the surface of the obtained silicon oxide vapor-deposited film has an ionic intensity of 10 or more, as determined by time-of-flight secondary ion mass spectrometry, where 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 10 or more, and / or the ratio of ionic intensity AO to ionic intensity S (ionic intensity AO / ionic intensity S) is 0.7 or more. By setting 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) to ionic intensity S to ionic intensity S (ionic intensity AO / ionic intensity S) to 0.7 or more, a molded article coated with a silicon oxide vapor-deposited film with high oil repellency can be obtained.

[0029] Furthermore, it is preferable that the ratio of ionic intensity A to ionic intensity S (ionic intensity A / ionic intensity S) at the peak is 8 or greater.

[0030] Furthermore, the ionic strengths S, A, and AO are as described above in [Silicon Oxide Vapor Deposition Film], and the preferred range for the ratio of the sum of ionic strengths A and AO to ionic strength S ((ionic strength A + ionic strength AO) / ionic strength S), the preferred range for the ratio of ionic strength AO to ionic strength S (ionic strength AO / ionic strength S), and the preferred range for the ratio of ionic strength A to ionic strength S (ionic strength A / ionic strength S) are also as described above in [Silicon Oxide Vapor Deposition Film].

[0031] (Organosilicon compounds and oxidizing gases) The present invention's method for manufacturing molded articles utilizes organosilicon compounds as silicon sources for silicon oxide vapor deposition film formation, including organosilicon compounds such as hexamethyldisilane, vinyltrimethylsilane, methylsilane, dimethylsilane, tetramethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, methyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane, as well as organosilicon compounds such as octamethylcyclotetrasiloxane, 1,1,3,3-tetramethyldisiloxane, and hexamethyldisiloxane. 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) and silicon tetrachloride can be used in combination with the above-mentioned organosilicon compounds. As organosilicon compounds, those having only a carbon-containing organic functional group selected from methyl, methoxy, ethyl, and ethoxy groups are preferred, organosilicon compounds having an ethoxy and / or methoxy group are more preferred, and organosilicon compounds having only an ethoxy group are even more preferred. Tetraethoxysilane, tetramethyldisiloxane, hexamethyldisilazane, etc. are preferred, and tetraethoxysilane is more preferred.

[0032] Oxygen or NOx is used as the oxidizing gas, with oxygen being preferred. Argon or helium are used as the carrier gas.

[0033] The present invention's method for manufacturing molded articles preferably involves coating the molded article with a silicon oxide vapor-deposited film using a plasma CVD method in which the ratio of the flow rate (volume) of the oxidizing gas to the total flow rate (volume) of the reaction gas is 0 to 65% by volume. By using these conditions, a silicon oxide vapor-deposited film with particularly excellent oil repellency can be obtained. The ratio of the flow rate (volume) of the oxidizing gas to the total flow rate (volume) of the reaction gas is more preferably 1 to 60% by volume or 1 to 50% by volume, even more preferably 2 to 40% by volume or 2 to 30% by volume, and most preferably 5 to 10% by volume. The flow rate of the reaction gas depends on the coating area of ​​the molded article to be processed, but for example, when coating the inner surface of a plastic container with a capacity of 400 to 1 L, it is preferable to supply a flow rate of 3 to 2000 sccm, particularly 5 to 600 sccm, per container. "Sccm" refers to the amount of gas (cc) flowing per minute at 0°C and 1 atmosphere.

[0034] (Plasma treatment) In this invention, plasma treatment is performed on the surface of a substrate held in a plasma treatment chamber by plasma CVD in an atmosphere containing the above-mentioned organosilicon compound, an oxidizing gas, and optionally a carrier gas, to form a deposited film with the aforementioned composition.

[0035] During plasma processing, the plasma processing chamber is preferably maintained at a vacuum level that generates a glow discharge. The pressure during film deposition is preferably 1 to 200 Pa, more preferably 3 to 100 Pa. In this state, a silicon oxide vapor-deposited film is formed by glow discharge using microwaves or high-frequency waves. For example, the microwave output is preferably in the range of 10 to 1000 W, more preferably 20 to 1000 W. The high-frequency output is preferably 20 to 1500 W, more preferably 30 to 1500 W.

[0036] In the present invention, the outermost layer of the molded article may be 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 manufacturing conditions. Alternatively, the conditions of the plasma CVD method may be changed, such as by changing the amount of oxidizing gas supplied, and the final coating may be applied under the above manufacturing conditions. [Examples]

[0037] Next, the present invention will be described in more detail with reference to examples, comparative examples, and reference examples, but the present invention is not limited in any way to these. Also, in the following, "%" refers to mass % unless otherwise specified. 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", and "AO / A" means "Ionic strength AO / A".

[0038] [Analysis method] (Surface functional group analysis) The sample surface was analyzed using a time-of-flight secondary ion mass spectrometer (TOF.SIMS5, sold by Hitachi High-Tech Science Corporation, with a measurement area of ​​500 μm square and a primary ion source of Bi (bismuth)). From the obtained peak ionic intensities, the ratio of the sum of ionic intensities A and ionic intensities 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), and the ratio of ionic intensity AO to ionic intensity A (ionic intensity AO / ionic intensity A) were calculated. The ion intensity (ionic strength) 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 strength S is defined as the intensity of the positive ion at m / z 43.97, ionic strength 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, and ionic strength 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.

[0039] (contact angle) A contact angle meter ("DMo-502," manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the contact angle using the "contact angle measurement [droplet method]" setting. The liquid used was refined rapeseed oil ("Nisshin Canola Oil," manufactured by Nisshin Oillio Group, Ltd.), and the amount of liquid used for each measurement was 2.0 μL. A "Teflon-coated needle" (manufactured by Kyowa Interface Science Co., Ltd.) was used to supply the oil to the contact angle meter. Because the oil has high viscosity and spreads over time after application to the sample surface, the value at 50 seconds after application, when the contact angle stabilizes to a certain extent, was recorded. The θ / 2 method was used for the analysis (the droplet radius r and height h are determined by image processing, and θ is calculated as θ = 2arctan(h / r)).

[0040] (film thickness) The thickness of the silicon dioxide vapor-deposited film was measured by one of the following methods. Method 1: Measurement was performed using a microscopic automated film thickness measurement system (model number: F54 XY 200UV, manufactured by Filmetrix). Method 2: Using a stylus-type film thickness gauge (DEKTAK, Bruker), the film thickness of the monitor glass deposited under the same conditions was measured and determined to be equivalent to the film thickness of the PET surface. Method 3: A cross-sectional sample was prepared using a cross-sectional sample preparation device (model: Cross-section Polisher IB-19510CP, manufactured by JEOL Ltd.), and the cross-section was observed and measured using a field emission scanning electron microscope (FE-SEM) (model: JSM-7800F Prime, manufactured by JEOL Ltd., magnification 30,000x, acceleration voltage 2kV, working distance 10.3mm).

[0041] (sliding) A silicon dioxide vapor-deposited film sample was placed on a stage ("Stage (Angular Inclination)" manufactured by AS ONE Corporation) set at a 70° inclination relative to the vertical. One drop (approximately 24.36 mg) of refined rapeseed oil colored with carotene ("Nisshin Canola Oil" manufactured by Nisshin Oillio Group Ltd., 99.9%, ("β-Carotene 30% FS" manufactured by DMS Corporation, 0.1%)) was dropped onto the surface of the silicon dioxide vapor-deposited film sample using a dropper, and the time it took for the trailing end of the droplet (the point of contact between the droplet and the silicon dioxide vapor-deposited film sample surface, where the droplet is located at the highest point) to travel 6 mm across the surface of the silicon dioxide vapor-deposited film sample was measured. The temperature during measurement was room temperature (23°C). Based on the travel time, evaluations from A to E were performed. If the evaluation was A to D, it was confirmed that there was an oil-repellent effect. Furthermore, the shorter the travel time, the higher and better the oil-repellent effect. A rating: Under 10 seconds Grade B: 11-20 seconds C rating: 21-60 seconds D rating: 61-300 seconds E rating: 301 seconds or longer

[0042] [Comparative Example 1 and Examples 1-3] (Silicon oxide vapor-deposited film and molded product) A 2 cm square PET sheet was cut from the flat portion of a commercially available polyethylene terephthalate (PET) container for edible oil, which had been coated with a silicon oxide vapor deposition film by plasma CVD using an organosilicon compound containing a methyl group and oxygen, and this was used as the sample for Comparative Example 1. In addition, a 2 cm square PET sheet was cut from the flat portion of an uncoated commercially available polyethylene terephthalate (PET) container for edible oil, and this PET sheet was coated with a silicon oxide vapor deposition film by plasma CVD, and this was used as the samples for Examples 1 to 4. The obtained samples were analyzed and evaluated, and the ratio of the sum of ionic strengths A and AO to ionic strength S ((ionic strength A + ionic strength AO) / ionic strength S), the ratio of ionic strength AO to ionic strength S (AO / S), the ratio of ionic strength A to ionic strength S (ionic strength A / ionic strength S), the ratio of ionic strength AO to ionic strength A (ionic strength AO / ionic strength A), film thickness, contact angle, and slipperiness are shown in Table 1.

[0043] [Table 1]

[0044] In Comparative Example 1, the sliding behavior was such that the 6 mm movement of the rear end did not complete even after more than 6 minutes. As shown in Table 1, the samples of Examples 1 to 3 had better sliding behavior than the sample of Comparative Example 1. From this, it can be confirmed that the samples of Examples 1 to 3 have high oil repellency. Examples 2 and 3, in particular, showed excellent oil repellency.

[0045] [Examples 4-9] (Silicon oxide vapor-deposited film and molded product) A 2 cm square PET sheet was cut from the flat surface of a commercially available, uncoated polyethylene terephthalate (PET) container for edible oil. Using a plasma CVD apparatus (model: PD-2201LC, manufactured by Samco Co., Ltd.), tetraethoxysilane (hereinafter referred to as TEOS) and oxygen (O2) were used as reaction gases, and the PET sheet was coated with a silicon oxide vapor-deposited film according to the plasma CVD conditions shown in Table 2, to be used as samples for Examples 4 to 9. The obtained samples were analyzed and evaluated, and the ratio of the sum of ionic strengths A and AO to ionic strength S ((ionic strength A + ionic strength AO) / ionic strength S), the ratio of ionic strength AO to ionic strength S (ionic strength AO / ionic strength S), the ratio of ionic strength A to ionic strength S (ionic strength A / ionic strength S), the ratio of ionic strength AO to ionic strength A (ionic strength AO / ionic strength A), film thickness, contact angle, and sliding properties are shown in Table 2.

[0046] [Table 2]

[0047] As shown in Table 2, the samples from Examples 4-9 exhibited better sliding properties and higher oil repellency compared to the sample from Comparative Example 1 in Table 1. In particular, Examples 4-6, which had a low O2 ratio (%) in the reaction gas during plasma CVD treatment, had a high ratio of ionic strength AO to ionic strength A (ionic strength AO / ionic strength A) (high alkoxy group content), resulting in significantly superior oil repellency compared to Examples 1-3 in Table 1.

Claims

1. The surface of the silicon dioxide vapor-deposited film has an ionic intensity of 10 or more, obtained by time-of-flight secondary ion mass spectrometry, where 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 10 or more, and / or the ratio of ionic intensity AO to ionic intensity S (ionic intensity AO / ionic intensity S) is 0.7 or more. Silicon oxide vapor-deposited film. (however, The ionic intensity S is the intensity of a positive ion with m / z 43.

97. Ionic 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. 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, m / z 102.97, and m / z 134.

96.

2. The ratio of the ionic strength AO to the ionic strength A (ionic strength AO / ionic strength A) is 0.2 or more. The silicon oxide vapor-deposited film according to claim 1.

3. A molded article whose surface is coated with a silicon oxide vapor-deposited film according to either claim 1 or 2.

4. The molded article according to claim 3, wherein the molded article is formed from a material selected from resin, glass, and metal, and is a container, pipe, or cooking utensil.

5. The molded article according to claim 4, wherein the contact angle of refined rapeseed oil at 20°C on the surface of the molded article covered with a silicon dioxide vapor-deposited film is 20° or more.

6. By using a plasma CVD method with an organosilicon compound and an oxidizing gas as the reaction gas, the molded product is coated with a silicon oxide vapor-deposited film. The surface of the obtained silicon oxide vapor-deposited film has an ionic intensity of 10 or more, as determined by time-of-flight secondary ion mass spectrometry, where 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 10 or more, and / or the ratio of ionic intensity AO to ionic intensity S (ionic intensity AO / ionic intensity S) is 0.7 or more. A method for manufacturing molded products coated with a silicon oxide vapor-deposited film that has high oil repellency. (however, The ionic intensity S is the intensity of a positive ion with m / z 43.

97. Ionic 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. 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, m / z 102.97, and m / z 134.

96.

7. The ratio of the ionic strength AO to the ionic strength A (ionic strength AO / ionic strength A) is 0.2 or more. A method for manufacturing a molded article according to claim 6.

8. The molded product is coated with a silicon oxide vapor-deposited film using a plasma CVD method in which the ratio of the flow rate (volume) of the oxidizing gas to the total flow rate (volume) of the reaction gas is 0 to 65% by volume. A method for manufacturing a molded article according to claim 6 or 7.

9. The organosilicon compound is an organosilicon compound having an ethoxy group and / or a methoxy group as an organic functional group containing carbon. The oxidizing gas is oxygen. A method for manufacturing a molded article according to claim 6 or 7.

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