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    • 专利摘要:
    water and oil repellent coating film and articles having this coating film. the invention relates to a coating film which can more reliably exhibit excellent water repellency and excellent oil repellency. this water and oil repellent coating film is a coating film formed on a surface of a material to impart water repellency and oil repellency, where (1) the coating film contains a composite particle containing metal oxide ; (2) the composite particle contains a) a metal oxide particle and b) a cover layer which contains a poly(fluoroalkyl methacrylate) resin and is formed on the surface of the metal oxide particle; and (3) a value obtained by dividing the fluorine content (% by weight) of the composite particle by a surface area (m 2 /g) of the metal oxide particle is 0.025 to 0.180.
    公开号:BR112014016192B1
    申请号:R112014016192-5
    申请日:2013-06-07
    公开日:2021-07-20
    发明作者:Kazunori Yamada；Tomonobu Sekiguchi；Hiroyuki Nishikawa；Hiroshi OE；Yuya Terasawa；Masahiko Kamada；Toshio Morii；Yusuke Tosaki；Yukiya Yamashita
    申请人:Toyo Aluminium Kabushiki Kaisha；Nippon Aerosil Co., Ltd.；
    IPC主号:
    专利说明:

    TECHNICAL FIELD
    [001] The present invention relates to a water and oil repellent coating film, and to articles having this coating film. BACKGROUND TECHNIQUE
    [002] A variety of items, eg, packaging materials (eg, containers, wrapping paper, trays, tubes, bags, and pouches), as well as frames, fabrics, and toys, are known as articles whose surface has been provided with water repellency and oil repellency. The packaging materials are used with, for example, food, beverages, medicines, cosmetics, and chemicals such as jelly sweets, puddings, yoghurts, liquid cleaners and detergents, toothpaste, curry roux, syrups, petroleum jelly, facial cleansing creams, and facial cleansing mousse. In addition, matter can take many forms, such as solid, semi-solid, liquid, viscous material, and gel. Water repellency or oil repellency is imparted, in accordance with the nature of the matter, to the surface in contact with the matter, to prevent the fixation of the matter to the greatest extent possible.
    [003] For example, methods are used in which the coating is carried out with, for example, a fluorinated compound as a means to impart water repellency and oil repellency.
    [004] For example, the oil-resistant packaging material disclosed in Patent Document 1 is prepared by laminating at least the following three layers, in the indicated sequence: (A) a thermoplastic resin layer, in which the surface pores top (x) having a pore diameter of 0.2 to 0.6 mm has been made in advance; (B) an oil resistant paper incorporating an oil resistance agent in which the number of carbons in the perfluoroalkyl group is less than 8; and (C) a layer of heat-sealable thermoplastic resin, on which the back surface pores (y) having a pore diameter of 0.2 to 0.6 mm have been made in advance.
    [005] Patent Document 2 provides a water and oil repellent base material which characteristically comprises the following first layer formed on a surface of a base material and the following second layer formed on the surface of the first layer: for the first layer, a layer containing fine silica particles of the product cured from a curable ink; for the second layer, a layer formed from a composition in which the essential components are a fluorosilicone compound and a solvent, or a layer formed from the cured product of such a composition.
    [006] Patent Document 3 discloses a conditioning material for a deoxygenating agent, an ethanol pervaporating agent, or a desiccant to preserve the freshness of the food. This packaging material is characterized by a two-layer coating provided by first coating the surface on at least one side of an air permeable paper base material with a clear paint of the urethane type or of the vinyl acetate chloride type using a curing agent of the isocyanate type and then applying a water and oil repellent of the fluorine type over this layer of clear paint of the urethane type or of the vinyl acetate type.
    [007] Regarding the technique of coating with such fluorinated compounds, methods have also been introduced in which the coating is carried out with a liquid dispersion that contains fine particles and an oil repellent agent.
    [008] For example, a method of producing an oil repellent coated article is disclosed in Patent Document 4, where this method characteristically comprises (1) a first step in which fine particles having a hair particle diameter are produced. minus 100 nm by the sol-gel method and (i) an article to be coated is immersed in a liquid dispersion in which the fine particles are dispersed and is removed and dried or (ii) a liquid dispersion in which the fine particles are dispersed is sprayed onto the article to be coated and drying is carried out; and (2) a second step in which (i) the article to be coated is then immersed in a liquid dispersion which contains fine particles with a diameter of 7 to 90 nm and a perfluoroalkylsilane, as an oil repellent agent, and is removed and dried or (ii) the article to be coated is sprayed with a liquid dispersion containing fine particles with a particle diameter of 7 to 90 nm and an oil repellent agent and drying is carried out.
    [009] Patent Document 5 discloses a water and oil repellent coated article, which is a coated article obtained by applying a coating composition containing alcohol, an alkoxysilane, a perfluoroalkylsilane, fine silica particles , a catalyst that promotes the hydrolysis reaction of alkoxysilanes, and water, where the root mean square value (RMS) of the irregularity for the surface of this coated article is at least 100 nm.
    [0010] Patent Document 1: Japanese Patent Application Publication No. 2011-73744
    [0011] Patent Document 2: Japanese Patent Application Publication No. 2000-169835
    [0012] Patent Document 3: Japanese Patent Application Publication No. 2009-191407
    [0013] Patent Document 4: Japanese Patent Application Publication No. 2011-140625
    [0014] Patent Document 5: Japanese Patent Application Publication No. 2010-89373
    [0015] However, although the technique described in these patent documents does indeed achieve a certain degree of water repellency or oil repellency, in order to promote a more practical implementation, it is still necessary to adopt a method that can effect more reliably. reliably satisfactory water repellency and oil repellency. DISCLOSURE OF THE INVENTION
    [0016] Consequently, the main objective of the present invention is to provide a coating film that can more reliably exhibit excellent water permeability and excellent oil permeability.
    [0017] As a result of extensive and intensive investigations in view of the problems with the prior art, the inventor discovered that this objective could be achieved by using a coating film that contained specific particles. The present invention has been completed based on this discovery.
    [0018] That is, the present invention relates to the water and oil repellent coating film described in the following.
    [0019] A water and oil repellent coating film that is a coating film formed on a surface of a substance to impart water repellency and oil repellency, where
    [0020] the coating film contains a composite particle containing metal oxide;
    [0021] the metal oxide-containing composite particle contains a) a metal oxide particle and b) a cover layer which contains a poly(fluoroalkyl methacrylate) resin and is formed on the surface of the metal oxide particle; and
    [0022] a value produced by dividing the fluorine content (% by weight) of the composite particle containing metal oxide by a surface area (m 2 /g) of the metal oxide particle is 0.025 to 0.180.
    [0023] The water and oil repellent coating film according to item 1, where a value produced by dividing the carbon content (% by weight) of the composite particle containing metal oxide by the surface area (m2/ g) of the metal oxide particle is 0.05 to 0.400.
    [0024] The water and oil repellent coating film according to item 1 or 2, where an average primary particle diameter of the metal oxide particle is 5 to 50 nm.
    [0025] The water and oil repellent coating film according to any of items 1 to 3, where the metal oxide particle is at least a selection from silicon oxide particles, aluminum oxide particles, and titanium oxide particles.
    [0026] The water and oil repellent coating film according to any of items 1 to 4, where the cover layer does not contain a silicon component.
    [0027] The water and oil repellent coating film according to any of items 1 to 5, where the coating film is porous.
    [0028] The water and oil repellent coating film according to any of items 1 to 6, where the surface of the coating film forming the outermost surface has an irregular structure that is produced by the composite particle containing metal oxide .
    [0029] The water and oil repellent coating film according to any of items 1 to 7, wherein the composite particle content containing metal oxide in the coating film is 10 to 100% by weight.
    [0030] The water and oil repellent coating film according to any of items 1 to 8, wherein the coating film additionally contains an adhesive component.
    [0031] A packaging material comprising the water and oil repellent coating film according to any of items 1 to 9.
    [0032] The packaging material according to item 10, comprising the water and oil repellent coating film according to any of items 1 to 9, a thermal sealing layer, and a layer of base material in the sequence indicated.
    [0033] The packaging material according to item 11, where all or a part of the water and oil repellent coating film present over a region that undergoes heat sealing is incorporated in the heat sealing layer when the heat sealing is performed .
    [0034] The water and oil repellent coating film according to any of items 1 to 9, where the coating film is obtained by a method comprising a step of coating a surface of the substance with a dispersion in which the particle composite containing metal oxide is dispersed.
    [0035] A method of producing a packaged product in which a material is filled in a container, the method of producing the packaged product comprising:
    [0036] a step of filling the material in the container; and
    [0037] a step of sealing the material by using the packaging material according to item 11 as a seal and sealing it with heat while abutting the water and oil repellent coating film of the packaging material in the opening in the container.
    [0038] The production method according to item 14, where all or a part of the water and oil repellent coating film, present over the region where the packaging material will be heat sealed, is incorporated in the sealing layer when thermal sealing is performed.
    [0039] The production method according to item 14, where the water and oil repellent coating film is not formed and the heat seal layer is exposed in the region where the packaging material will be heat sealed.
    [0040] The production method according to any of items 14 to 16, where the matter exhibits fluidity.
    [0041] The method of production according to any of items 14 to 17, where the matter is a liquid.
    [0042] The production method according to any of items 14 to 18, where the matter contains a fraction of water and/or an oil component.
    [0043] The production method according to any of items 14 to 19, where the viscosity of the matter at 20°C is 0.01 to 500 dPa.s. Advantages of the invention
    [0044] Through the use of a composite particle containing metal oxide, which has a special covering layer, the present invention can provide a coating film that more reliably produces excellent water repellency and excellent oil repellency . In particular, when a microscopic and complex irregular structure is formed on the surface of the coating film by a plurality of composite particles containing metal oxide in succession, even better water repellency and oil repellency can be obtained by a synergistic action between this irregular structure and the covering layer.
    [0045] The coating film having these characteristic qualities can be favorably used with, for example, packaging materials, tableware, cooking utensils, kitchen utensils, household items, clothing, construction products, structures, and equipment carriage. It can be particularly favorably used with packaging materials, starting with seals, but also including, for example, molded containers, wrapping paper, trays, tubes, and bags such as sacks and pouches. In the case of use with packaging materials, the material may be a material containing an aqueous liquid and/or an oily liquid. That is, a material that exhibits fluidity can be used. More specifically, the coating film having these characteristic qualities is useful for packaging materials to preserve various types of materials, for example, foods such as curry, stew, yogurt, jelly sweets, pudding, and condiments (e.g., seasonings for grilled meats and sauces), and also, for example, liquid cleaners and detergents, toothpastes, cosmetics such as facial cleansing creams and facial cleansing mousse, and medicines. BRIEF DESCRIPTION OF THE DRAWINGS
    [0046] Figure 1 is a schematic diagram of a composite particle containing metal oxide of the present invention;
    [0047] Figure 2 is a schematic diagram of a coating film of the present invention;
    [0048] Figure 3 is a diagram showing the layer structure of a packaging material that includes a coating film of the present invention; and
    [0049] Figure 4 shows the results of observing the surface of the coating film according to Example 2-4. EXPLANATION OF REFERENCE NUMBERS 11 composite particle containing metal oxide 12 coating layer 13 metal oxide particle (aggregate) 21 coating film 22 substance 23 pore 24 coating film surface 31 packaging material 32 heat sealing layer 33 material base in sheet form 34 laminated BEST WAY TO CARRY OUT THE INVENTION
    [0050] The water and oil repellent coating film of the present invention is a coating film formed on a surface of a substance (an article) in order to impart water repellency and oil repellency, where
    [0051] the coating film contains a composite particle containing metal oxide;
    [0052] the composite particle containing metal oxide contains a) a metal oxide particle and b) a cover layer containing a poly(fluoroalkyl methacrylate) resin and is formed on the surface of the metal oxide particle; and
    [0053] the value produced by dividing the fluorine content (% by weight) of the composite particle containing metal oxide by the surface area (m 2 /g) of the metal oxide particle is 0.025 to 0.180.
    [0054] A schematic diagram of the metal oxide-containing composite particle is shown in Figure 1. As shown in Figure 1, the metal oxide-containing composite particle 11 comprises a metal oxide particle 13 as a core and a cover layer 12 formed on the surface of the metal oxide particle 13. The core metal oxide particle 13 as a core forms an aggregate structure (porous aggregate structure) in which a plurality of metal oxide particles (primary particles) is united three-dimensionally. Covering layer 12 is formed on the inside and on the outer shell of this aggregate structure. In figure 1, this aggregate structure is shown schematically in a spherical shape and the covering layer 12 is indicated on the outer cladding only. A coating film 21 containing the metal oxide-containing composite particle 11 is shown schematically in Figure 2. The coating film 21 is formed on the surface of a substance 22 and includes the metal oxide-containing composite particles 11 and the spaces 23 formed between these particles. The surface 24 (outer surface) of the coating film 21 desirably forms an irregular structure (irregular surface) due to the plurality of composite particles containing metal oxide 11. That is, to obtain even greater water repellency and oil repellency The coating film of the present invention preferably has an irregular structure formed by the metal oxide particles on the surface of the coating film.
    [0055] Thereby, a high water repellency and a high oil repellency are exhibited due to an interaction between the irregular surface 24 described above and the cover layer 12 containing a poly(fluoroalkyl methacrylate) resin and formed on the surface of the metal oxide-containing composite particle 11. In addition, the coating film of the present invention can provide uniform water repellency and oil repellency over the entire surface of the coating film, because all of the composite particles containing metal oxide present in the coating film of the present invention are covered by a determined amount of the coating layer 12 containing a poly(fluoroalkyl methacrylate) resin. In other words, because the individual metal oxide-containing composite particles have the cover layer 12 in a sufficient amount for the development of a high water repellency and a high oil repellency, a high water repellency and a high repellency to oil are displayed over the entire coating film evenly and, as a result, a uniform water repellency and a uniform oil repellency are imparted to the substance 22.
    [0056] Even in the case of a material (particularly an aqueous or oily liquid) that would stick to the outer surface of a coating film, such material is repelled by the water repellency and oil repellency of the coating film of the present. invention and, as a result, the adhesion of such material to the coating film 21 can be prevented. the substance
    There is no particular limitation on the substance that is the target for forming the coating film of the present invention (i.e., the target of water repellency and oil repellency). The substance can be, for example, a metal, plastic, ceramic, rubber, fibrous material (paper, non-woven fabric, fabric, and so on), or a composite material thereof. It can be a finished product, semi-finished product, or a starting material for them.
    [0058] More specifically, this substance (finished product and so on) can be a wide variety of materials as used for, for example, packaging materials, household products (for example, lenses, rain gear, luggage or briefcases) , construction materials (eg, roofing materials, wallpaper, flooring, ceiling lining materials, tile, and enamel), tableware, cooking utensil (eg, casseroles or pots, drip trays for tops from gas ovens, oil shield panels, and top plates to induction oven tops), kitchen utensils, sports products, clothing (eg, caps or hats, shoes, gloves, and coats), structures (by example, building walls, bridges, and towers), transportation equipment (surfaces of external bodies for, for example, vehicles, motorcycles, railway cars, and boats), cosmetics, medicines, toys, and industrial tools. identification.
    Packaging materials are particularly suitable as the substance in the present invention. These packaging materials include both the packaging as a finished product (completed product) and the starting materials for packaging. The finished product (completed product) can be exemplified primarily by container lids or closures, but also by packaging, such as molded containers, wrapping paper, trays, tubes, and bags (bags and so on). The starting material for the packaging can be exemplified by the base material and a laminate containing a heat seal layer. That is, it can be exemplified by a packaging material comprising the water and oil repellent coating film of the present invention, a thermal sealing layer, and a base material in the indicated sequence (this is a packaging material according to the present invention). Embodiments of representative examples of packaging materials in accordance with the present invention are given below. The coating film
    [0060] The coating film according to the present invention contains composite particles containing metal oxide. The content of the metal oxide-containing composite particles in the coating film can be adjusted, as appropriate, in accordance with, for example, the desired water repellency and oil repellency, but is generally preferably 10 to 100% in weight is particular and preferably is 30 to 100% by weight. That is, proportionally greater water repellency and oil repellency can be obtained in the present invention as the content of the composite particles containing metal oxide increases to 100% by weight.
    [0061] The amount of application of the coating film (weight after drying) to the substance is not limited and can be established, as appropriate, in accordance with, for example, the desired water and oil repellency, the content of composite particles containing metal oxide, and so on, but it can in general be set in the range of 0.01 to 30 g/m2 and in particular it can be set in the range of 0.1 to 30 g/m2. Consequently, for example, it can be favorably adjusted in the range of about 1 to 30 g/m2 and particularly in the range of 2 to 8 g/m2.
    [0062] The composite particle containing metal oxide and its preparation
    [0063] The composite particle containing metal oxide
    [0064] The metal oxide-containing composite particle contains a) a metal oxide particle and b) a cover layer which contains a poly(fluoroalkyl methacrylate) resin and is formed on the surface of the metal oxide particle.
    [0065] The metal oxide particle according to a) above must be able to form the core of the composite particle containing metal oxide, but it is not normally limited and, for example, at least one particle can be used ( powder) selected from silicon oxide, titanium oxide, aluminum oxide, zinc oxide, and so on. At least one selection from silicon oxide particles, titanium oxide particles, and aluminum oxide particles is particularly preferred for the present invention. Known or commercially available metal oxide particles can be used for these metal oxide particles as such. The average primary particle diameter of the metal oxide particle is not limited but is generally 5 to 50 nm, although 7 to 30 nm is particularly desirable. Even better water repellency and oil repellency can be achieved by operating within this range of particle diameters.
    [0066] The average primary particle diameter of the metal oxide particle for the present invention can be measured using a transmission electron microscope or a scanning electron microscope. More specifically, the mean primary particle diameter can be determined by taking a photograph using a transmission electron microscope or a scanning electron microscope; measuring the diameter of at least 200 particles on this photograph; and calculating an arithmetic mean value from it.
    [0067] Known or commercially available products can be used for these nano-level metal oxide particles. Examples for silicon oxide are AEROSIL 200 (product name, "AEROSIL" is a registered trademark, product of Nippon Aerosil Co., Ltd. The same applies below.), AEROSIL 130, AEROSIL 300, AE-ROSIL 50, AEROSIL 200FAD, and AEROSIL 380. An example for titanium oxide is AEROXIDE TiO2 T805 (product name, product of Evonik-Degussa GmbH). An example for aluminum oxide is AEROXIDE Alu C 805 (product name, Evonik-Degussa GmbH product).
    [0068] The cover layer according to b) contains a poly(fluoroalkyl methacrylate) resin. The use of this resin results in the formation, on the particle surface, of a strong cover layer which has a relatively high tack due to an excellent affinity to the metal oxide particle (particularly the silicon oxide particle), and can also exhibit high water and oil repellency. Known or commercially available resins can be used for this resin. Commercially available products can be exemplified by CHEMINOX FAMAC-6 (product name, product of UNIMATEC Co., Ltd. (Japan)), Zonyl TH Fluoromonoer code 421480 (product name, product of Sigma-Aldrich (USA)), SCFC-65530-66-7 (product name, Maya High Purity Chemi (China) product), FC07-04 through -10 (product names, Fluory, Inc. (US) product), CB INDEX:58 ( product name, Wilshire Chemical Co., Inc. (USA) product), AsahiGuard AG-E530 and Asahi-Guard AG-E060 (product names, Asahi Glass Co., Ltd. products), TEMAc-N (name of product, product of Top Fluorochem Co., Ltd. (China)), Zonyl 7950 (product name, product of SIGMA-RBI (Switzerland)), 6100840 to 6100842 (product names, product of Weibo Chemical Co., Ltd. . (China)), and CB INDEX:75 (product name, product of ABCR GmbH & Co. KG (Germany)).
    Among the foregoing, for example, a copolymer obtained by the copolymerization of a) poly(fluoroethyl methacrylate), b) 2-N,N-diethylaminoethyl methacrylate, c) 2-hydroxyethyl methacrylate, and d) dim - 2,2'-ethylenedioxydiethyl taacrylate can be favorably used with this resin, to obtain even better water and oil repellency. A commercially available resin as referred to above can also be used here.
    [0070] In the present invention, the value (A value) obtained by dividing the fluorine content (% by weight) of the composite particle containing metal oxide by the surface area (m 2 /g) of the metal oxide particle is 0.025 to 0.180 and is preferably 0.030 to 0.175. Furthermore, the value (B value) obtained by dividing the carbon content (% by weight) for the composite particle containing metal oxide by the surface area (m 2 /g) of the metal oxide particle is desirably 0.05 to 0.400 and particularly 0.06 to 0.390. This carbon content and fluorine content are indices in the present invention that indicate the degree of coverage, and the higher numerical values for these indicate a greater amount of coverage. Excellent adhesion to the surface of the metal oxide particle and excellent water repellency and oil repellency can be obtained in the present invention by obeying the determined amounts of coating (the carbon content and the fluorine content and particularly the fluorine content ). The desired water repellency and oil repellency are not obtained when the value produced by dividing the fluorine content (% by weight) by the surface area (m2/g) of the metal oxide particle is less than 0.025. It is difficult to obtain the desired water repellency and oil repellency when the value produced by dividing the carbon content (% by weight) by the surface area (m2/g) of the metal oxide particle is less than 0. 05. On the other hand, the production of the composite particle containing metal oxide itself is quite problematic when the value produced by dividing the fluorine content (% by weight) by the surface area (m 2 /g) of the metal oxide particle exceeds 0.180. Furthermore, it is difficult to produce the composite particle containing metal oxide when the value produced by dividing the carbon content (% by weight) by the surface area (m 2 /g) of the metal oxide particle exceeds 0.400. Thus, the A value desirably obeys the given range to obtain excellent water repellency and oil repellency, and the B value desirably also obeys the given range to obtain even better water repellency and oil repellency.
    [0071] The carbon content in the composite particle containing metal oxide is measured in the present invention by the following method: a (sample) is heated to at least 800°C, in an oxygen atmosphere, to convert the carbon contained in the hydrophobic groups of the surface in CO2 and the carbon content present on the surface of the (sample) is determined with a microquantitative carbon analyzer. For the fluorine content in the composite particle containing metal oxide in the present invention, the sample is baked in a ring oven at 1000°C; the gas produced is recovered by steam distillation; and detection and quantification as the fluoride ion are carried out on the recovered solution by ion chromatography. The surface area (m2/g) (specific surface area) was determined by the one-point BET method using a Macsorb (from Mountech Co., Ltd.). 30% by volume nitrogen/70% by volume helium was used as the adsorption gas. Sample pre-treatment was performed by ventilating with adsorption gas for 10 minutes at 100°C. The cell containing the sample was then cooled with liquid nitrogen; the temperature was raised to room temperature after the end of adsorption; and the surface area of the sample was determined from the amount of nitrogen gas desorbed. The specific surface was determined by dividing by the sample mass.
    [0072] Preparation of composite particle containing metal oxide
    [0073] The method of producing the composite particle containing metal oxide is not particularly limited, and the covering layer can be formed on the metal oxide particle (powder) by, for example, a coating method or method of known granulation, using a poly(fluoroalkyl methacrylate) resin as the coating material. For example, the metal oxide-containing composite particle can be favorably produced by a production method which comprises a step (the coating step) of coating the metal oxide particle with a coating liquid in which a poly resin. Liquid (fluoroalkyl methacrylate) is dissolved or dispersed in a solvent.
    [0074] This production method can advantageously use a poly(fluoroalkyl methacrylate) resin which is a liquid at normal temperature (25°C) and normal pressure for the poly(fluoroalkyl methacrylate) resin. The commercially available products, provided above as examples, can also be used as this poly(fluoroalkyl methacrylate) resin.
    [0075] The solvent used in the coating liquid is not particularly limited and although water or an organic solvent such as alcohol or toluene can be used, the use of water is preferred for the present invention. That is, the coating liquid is preferably a coating liquid in which the poly(fluoroalkyl methacrylate) resin is dissolved and/or dispersed in water.
    [0076] The content of poly(fluoroalkyl methacrylate) resin in this coating liquid is not particularly limited, but preferably, in general, it ranges from 10 to 80% by weight, particularly from 15 to 70% by weight, and more particularly from 20 to 60% by weight.
    [0077] The method used to coat the coating liquid onto the surface of the metal oxide particle can be a known method and, for example, a spray method, an immersion method, an agitated granulation method can be used , and so on. In particular, coating by a spray method is particularly preferred in the present invention from the point of view of obtaining excellent uniformity.
    [0078] After the coating liquid has been applied, the composite particle containing metal oxide can be obtained by removing the solvent using a heat treatment. The heat treatment temperature is preferably in general about 150 to 250°C and particularly preferably it is 180 to 200°C. There is no limitation on the atmosphere for heat treatment, however, an inert (non-oxidizing) gas atmosphere is desirable, such as, for example, nitrogen gas, argon gas, and so on. For example, as needed, a sequence of steps comprising an additional coating step and a heat treatment step can be carried out one or more times. This can be used to implement favorable coverage amount control. 35 Other components in the coating film
    [0079] In addition to the composite particle containing metal oxide described above, the coating film of the present invention may contain other components, within a range in which the effects of the present invention are not impaired. Examples here are adhesives (eg, heat-sealing agents), colorants, dispersing agents, anti-fouling agents, viscosity modifiers, print protectants, and so on.
    [0080] In particular, in accordance, for example, with the type of article with which the coating film of the present invention is used, the incorporation of an adhesive (adhesive component) is effective to further increase the adhesive potency of the film of coating to the article and the adhesive strength between the composite particles containing metal oxides. There is no particular limitation on the adhesive that can be used in this case, and known and commercially available adhesives can be used. Examples here of adhesives (particularly heat sealing agents) such as polyolefin resins, polyester resins, polyurethane resins, epoxy resins, acrylic resins, and vinyl resins. More specifically, the following can be used as the heat sealing agent: low density polyethylene; medium density polyethylene; high density polyethylene; straight chain (linear) low density polyethylene; polypropylene; ethylene-vinyl acetate copolymers; ionomer resins; ethylene-acrylic acid copolymers; ethylene-ethyl acrylate copolymers; ethylene-methacrylic acid copolymers; ethylene-methyl methacrylate copolymers; ethylene-propylene copolymers; methylpentene polymers; polybutene polymers; acid-modified polyolefin resins, provided by modifying a polyolefin resin, for example, polyethylene or polypropylene, with an unsaturated carboxylic acid, such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, or acid itaconic; poly(vinyl acetate) resins; poly(meth)acrylic resins; polyacrylonitrile resins; poly(vinyl chloride) resins; other thermal adhesive resins; mixed resins from the foregoing; copolymers containing combinations of the monomers that make up the above-described polymers; and modified resins.
    [0081] When a heat-sealing agent is used, a coating film can be formed that exhibits even better adhesiveness to the surface of the substance, for example, by coating in "3. Method of forming the coating film " described below, using a liquid dispersion in which the particles (powder) of the heat sealing agent are dispersed with the composite particles containing metal oxide and, thereafter, melting the heat sealing agent in the heat treatment step in the " 3. Method of forming the coating film" described below. The content of the adhesive in the coating film, when an adhesive is used, can generally be adjusted as appropriate within the range of 20 to 80% by weight in the coating film. Method of forming the coating film
    [0082] The method of forming the coating film of the present invention is not particularly limited and, inter alia, known methods can be used. In particular, the coating film is favorably formed in the present invention by a method comprising a step of coating a surface of the substance with a liquid dispersion containing the composite particles containing metal oxides. That is, a water and oil repellent coating film can be obtained by coating it by a wet method and, after that, removing the solvent. When using a perfluoroalkylsilane, which is a repellent agent to water and fluorinated oil according to the prior art, a catalyst must be added or the pH of the water and oil repellent agent must be adjusted to control the reaction. of hydrolysis of the alkoxysilane group thereon; in contrast thereto, such a step may not be present in the present invention and a desired coating film may be formed relatively simply. Furthermore, the use of water or the like for the solvent makes it possible to also keep the load on the environment to a minimum.
    [0083] The solvent used in the liquid dispersion is not particularly limited and may be exemplified by water, alcohol (ethanol), cyclohexane, toluene, acetone, IPA, propylene glycol, hexylene glycol, butyl diglycol, pentamethylene glycol, normal- pentane, normal-hexane, hexyl alcohol, and so on.
    [0084] The amount of composite particles containing metal oxides, dispersed in the organic solvent, is generally established as appropriate in the range of about 20 to 50 g/L (liter), in accordance, for example, with the type of substance, the degree of water repellency and oil repellency, and so on.
    [0085] As indicated above under "2) Other components in the coating film", an adhesive (and particularly a heat sealing agent) may also be contained in the liquid dispersion. More specifically, particles of an adhesive component can be dispersed in the liquid dispersion. The adhesive components given above in "2) Other components in the coating film" can be used as this adhesive component. In addition, the other components given above under "2) Other components in the coating film" may also be contained in the liquid dispersion.
    [0086] The method for coating the liquid dispersion onto the surface of the material is not limited and known methods can be used. For example, any known method can be used, such as roller coating, gravure coating, bar coating, wiper coating, comma coating, partial coating, brushing, and so on.
    [0087] The amount of application during coating with the liquid dispersion is not limited, and the weight of the composite particle containing metal oxide after the coating has been dried can be adjusted as appropriate, for example within the range of 0, 01 to 30 g/m2 and preferably 0.1 to 30 g/m2. Consequently, it can be adjusted so as to provide, for example, about 50 to 600 mg/m2 and particularly 200 to 500 mg/m2.
    [0088] A drying step can be performed after the liquid dispersion has been coated onto the surface of the substance. This drying can be spontaneous drying or drying with the application of heat. In the case of drying with the application of heat, heating can in general be carried out at not more than 200°C and preferably at not more than 100°C.
    [0089] After the liquid dispersion has been coated onto the surface of the substance, a heat treatment step can also be carried out in the present invention, after the drying step or in place of the drying step. In particular, when a heat-sealing agent is contained in the liquid dispersion as an adhesive component, the coating film can be tightly affixed to the surface of the substance by melting the heat-sealing agent, subjecting the coating film onto the surface of the substance to a heat treatment. By doing this, a coating film can be formed for which there is better inhibition of exfoliation and flaking. The temperature of the heat treatment can be adjusted as appropriate, in accordance with, for example, the nature of the heat sealing agent being used, and can generally be within the range of about 150 to 250°C. There is no limitation on the atmosphere of the heat treatment, but the operation can generally be done in the atmosphere or in an oxidizing atmosphere. The properties of the coating film
    [0090] The water and oil repellent coating film of the present invention contains the composite particles containing metal oxides and, in particular, the surface of the coating film preferably has an irregular structure (an approximately fractal structure) formed by the particles composites containing metal oxides. More specifically, it desirably has a surface formed by spaces and the particles themselves, and which is formed by joining a plurality of composite particles containing metal oxides. By this structure together with the composite particle containing metal oxide having the determined covering layer, an even better water repellency and an oil repellency can be realized. That is, an even better water repellency and oil repellency can be obtained as a result of the surface with this irregular structure being substantially composed of this covering layer. In this case, particles, except the composite particle containing metal oxide, may be included within a range in which the useful effects of the present invention are not impaired, as particles contributing to the formation of the irregular structure. The irregular structure of the coating film surface can be observed using a scanning electron microscope. Example 2-4, infra, is shown in figure 4 as a representative example.
    [0091] The thickness of the coating film is not particularly limited, but in general can be adjusted, as appropriate, within the range of 0.5 to 30 µm. In particular, about 1 to 8 µm is preferred when the packaging material has a structure in which the coating film is embedded in the heat seal layer during heat sealing.
    [0092] With respect to the water repellency possessed by the coating film, the contact angle versus pure water (25°C) is generally preferably at least 140° and is particularly preferably at least 150°. With respect to oil repellency, the contact angle versus edible oil: olive oil (25°C) is preferably at least 130° and is particularly preferably at least 140°. Furthermore, although there is no limitation on the roll off angle (olive oil) for the coating film, it is generally preferably 5 to 20°. < Modalities of the present invention for packaging materials >
    [0093] Arrangements for the production of the packaging materials are given below, using a laminate containing a thermal sealing layer and a base material in sheet form as the substance in 1 mentioned above. As shown in Figure 3, in the packaging material 31, a coating film 21 is formed as the outermost layer on a laminate 34, on which a heat seal layer 32 is laminated so as to be in contact with a base material. in the form of sheet 33. Laminate Structure
    [0094] Known materials can be used for the base material in sheet form 33. For example, paper, synthetic paper, a resin film, a resin film containing a vapor deposited layer, an aluminum foil, or another sheet metal can be favorably used alone, or a composite material comprising the above-mentioned layer or a laminate comprising the above-mentioned layer can be favorably used.
    [0095] There is also no limitation on the lamination method for the base material in sheet form or on the method for laminating the base material in sheet form with the heat seal layer, and, for example, they can be known methods are used, for example, dry lamination methods, extrusion lamination methods, wet lamination methods, thermal lamination methods, and the like.
    [0096] The thickness of the base material in sheet form is not particularly limited, and the range used for known packaging materials can be used. For example, this is generally preferably about 1 to 500 µm.
    [0097] The heat seal layer 32 is arranged as the outermost (most superficial) layer of the laminate 34. Known heat seal layers can be used for the heat seal layer 32. For example, in addition to a known seal film, a layer formed of an adhesive, for example, a lacquer-type adhesive, an easy peel adhesive, or a hot melt adhesive, may be used.
    [0098] There is no limitation on the main component of the heat seal layer, and the same main components as for the heat sealing agents described above can be used. More specifically, the following can be used: low density polyethylene; medium density polyethylene; high density polyethylene; straight chain (linear) low density polyethylene; polypropylene; ethylene-vinyl acetate copolymers; ionomer resins; ethylene-acrylic acid copolymers; ethylene-ethyl acrylate copolymers; ethylene-methacrylic acid copolymers; ethylene-methyl methacrylate copolymers; ethylene-propylene copolymers; methylpentene polymers; polybutene polymers; acid-modified polyolefin resins, provided by modifying a polyolefin resin, for example, polyethylene or polypropylene, with an unsaturated carboxylic acid, such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, or acid itaconic; poly(vinyl acetate) resins; poly(meth)acrylic resins; polyacrylonitrile resins; poly(vinyl chloride) resins; other thermal adhesive resins; resins mixed from them; copolymers containing combinations of the monomers that make up the above-described polymer; and modified resins. With respect to the structure of the heat seal layer, a single layer of a sealing film may be used or a seal film composed of two or more layers may also be used, as provided by co-extrusion or extrusion lamination.
    [0099] The thickness of the heat seal layer is not particularly limited, however, considered in terms of productivity and cost, it is preferably about 1 to 100 µm and is more preferably about 3 to 50 µm. When the thermal sealing is performed, all or part of the coating film, present on the region undergoing thermal sealing, is embedded in the thermal sealing layer, in the packaging material of the present invention, and the thermal sealing can then be carried out due to the thermal seal layer is becoming more superficial. Because of this, the thickness is desirably adjusted to a thickness, within the range of thicknesses indicated above, at which the coating film can be embedded as much as possible in the heat seal layer.
    [00100] To the extent that the effects of the present invention are not impaired, the various layers employed in the packaging materials may, as necessary, be laminated, in a freely selected position, to the base material in sheet form in the laminate 34, for the purpose of providing various properties (eg resistance to moisture permeability, resistance to oxygen permeability, opacity, thermal insulation, impact resistance, and so on). Examples in this regard are a print layer, print protection layer (ie, each OP), colored layer, adhesive layer, adhesion reinforcing layer, basecoat layer, backing layer, antiskid agent layer , lubricating layer, and anti-fog agent layer. b) Formation of the coating film on the laminate surface
    [00101] Excellent water repellency and excellent oil repellency can be exhibited by the packaging material of the present invention when the coating film of the present invention is formed on the surface of the thermal sealing layer of the aforementioned laminate. That is, the coating film of the present invention is, in particular, preferably formed adjacent to the heat seal layer.
    [00102] The amount (weight after drying) of the coating film formed on the surface of the laminate is not limited, but in general it can be established, as appropriate, within the range of 0.01 to 30 g/m2 and preferably within the range of 0.1 to 30 g/m2. Adjusting the amount of bonding in this range makes it possible to obtain even better water repellency and oil repellency for a long time, and is also more cost-effective and inhibiting the peeling of the coating film. Consequently, for example, the amount of binding may be in the range of 0.01 to 10 g/m2, particularly 0.2 to 1.5 g/m2, and even more particularly 0.2 to 1 g/m2.
    [00103] The coating film preferably forms a porous layer in the present invention, and its thickness is preferably about 0.1 to 5 µm and is more preferably about 0.2 to 2.5 µm. Since a large amount of air can be contained in this layer, by joining the coating film in the form of such a porous layer, an even better water repellency and an oil repellency can then be exhibited.
    [00104] The surface of the coating film on the packaging material of the present invention also desirably has an irregular structure, formed by the union of composite particles containing metal oxides. This can achieve even better water repellency and oil repellency.
    [00105] The coating film can be formed on the entire surface on the side of the heat seal layer (the entire surface on the opposite side of the base material side in sheet form) or it can be formed in a region that excludes the region in which the heat-seal layer is heat-sealed (ie, the joint edge).
    [00106] Even in the case of joining the coating layer over the entire surface on the side of the thermal sealing layer, the thermal sealing is not substantially impaired in the present invention because all or a part of the coating film, present in the region that suffers heat seal, is sunk into this heat seal layer, and thus, from the industrial production point of view, it is preferred that the coating layer joins over the entire surface of the heat seal layer.
    [00107] The packaging material 31, for example, can be favorably produced by the following method. That is, the packaging material can be produced by a method of producing a packaging material that contains a base material in sheet form and a thermal sealing layer, where the method comprises a step (the step of forming the film of coating) in which the coating film is formed by coating a liquid dispersion containing the composite particles containing metal oxide, in a solvent, over all or a portion of the outermost surface of the heat seal layer in a laminate containing a base material in sheet form and a heat seal layer, where the heat seal layer is arranged as the outermost layer.
    [00108] In the coating film formation step, the coating film is formed by coating a liquid dispersion containing the composite particles containing metal oxide, in a solvent, over all or a part of the outermost surface of the veal layer. -thermal damage in a laminate comprising a base material in sheet form and a heat sealing layer, where the heat sealing layer is arranged as the outermost layer.
    [00109] The laminate described in a) above can be used as the laminate. Thereby, the same base material in the form of sheet, heat seal layer, and other layers as described above can be used.
    [00110] A liquid dispersion prepared by dispersing at least the composite particles containing metal oxide (powder) in a solvent is used as the liquid dispersion. The metal oxide-containing composite particle, described above in "1-1) The metal oxide-containing composite particle", can be used as the metal oxide-containing composite particle here.
    [00111] The solvent must not, in particular, degrade the composite particles containing metal oxide that are used, but it is not normally limited and, for example, may be selected, as appropriate, from organic solvents, for example, alcohol ( ethanol), cyclohexane, toluene, acetone, IPA, propylene glycol, hexylene glycol, butyl diglycol, pentamethylene glycol, normal-pentane, normal-hexane, and hexyl alcohol. There is no limitation on the amount of composite particles containing metal oxide dispersed in the solvent and, for example, this can be adjusted around 10 to 200 g/L. Consequently, it can also be adjusted, for example, within the range of 10 to 100 g/L.
    [00112] Within a range in which the advantages of the present invention are not impaired, the liquid dispersion in the present invention may, as appropriate, incorporate other additives as needed. For example, a dispersing agent, colorant, antifouling agent, viscosity modifier, and so on, can be added. In addition, as indicated above, the powder of an adhesive (particularly a heat-sealing agent) can also be dispersed in this liquid dispersion to further enhance the adhesive strength of the coating film.
    [00113] Any known method, for example, cylinder coating, gravure coating, bar coating, wiper coating, comma coating, partial coating, brushing, and so on, can be employed as the method of coating to apply the liquid dispersion. When, for example, roller coating or the like is used, a coating step can be carried out by forming the coating film on the heat seal layer, using a liquid dispersion prepared by dispersing at least the composite particles containing oxide. metal in a solvent.
    [00114] After the coating film formation step, a step of drying the coating film can be carried out before a heating step. This drying method can be spontaneous drying or forced drying (heat application). In the case of drying with the application of heat, a temperature in general of not more than 200°C and preferably not more than 100°C can be used.
    [00115] After the liquid dispersion has been coated on the surface of the substance, a heat treatment step can also be performed in the present invention, after the drying step or in place of the drying step. In particular, when a heat-sealing agent is contained in the liquid dispersion as an adhesive component, the coating film can be firmly affixed to the surface of the substance by melting the heat-sealing agent, subjecting the coating film onto the surface of the substance to a heat treatment. By doing this, a coating film can be formed for which there is better inhibition of exfoliation and flaking. The temperature of the heat treatment can be adjusted as appropriate, in accordance with, for example, the nature of the heat sealing agent being used, and can generally be within the range of about 150 to 250°C. There is no limitation on the atmosphere of the heat treatment, but the operation can generally be done in the atmosphere or in an oxidizing atmosphere.
    [00116] The obtained packaging material can be used as such or can be used after it has been subjected to processing. The same methods as used with known packaging materials can be used for the processing method. For example, a stamping process, a semi-cutting process, a carving process, and so on can be performed. The packaging material of the present invention can be favorably used most prominently for lids or closures, but also for, for example, molded containers, wrapping paper, trays, tubes, and bags such as sacks and pouches. EXAMPLES
    [00117] The characteristic qualities of the present invention are more specifically described through the examples and comparative examples provided below. However, the scope of the present invention is not limited to or by the examples. Example 1-1
    [00118] Production of composite particle containing metal oxide
    [00119] 100 g of a silica fume powder having an average primary particle diameter of 12 nm and a BET specific surface area of 200 m2/g (product name: AEROSIL 200, from Nippon Aerosil Co., Ltd .), were introduced into a reactor and were sprayed with 500 g of a surface treatment agent, while stirring under an atmosphere of nitrogen gas. This was followed by stirring for 30 minutes at 200°C and then cooling. A powder of fine surface-modified silica particles (composite particles containing fine metal oxide) was thereby obtained. A water-based dispersion (solids content: 20% by weight) of a copolymer of poly(fluoroethyl methacrylate), 2-N,N-diethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, and dimethacrylate 2,2'-ethylenedioxydiethyl was used as the treating agent here. The carbon content and the fluorine content of the obtained surface-modified fine silica particles (powder) are shown in Table 1. (2) Production of the liquid dispersion
    [00120] 30 parts by weight of the fine surface-modified silica particles obtained in (1) described above were added to 200 parts by weight of ethanol, with mixing, to prepare a liquid dispersion. (3) Formation of the coating film
    [00121] Using a co-extruded film, composed of poly(ethylene terephthalate) (thickness = 12 μm) / polyurethane type dry laminated adhesive / aluminum foil (20 μm) / polyurethane type dry laminated adhesive / (polyethylene/polypropylene) as a laminate, the liquid dispersion prepared in the above-mentioned (2) was coated with a rod coater on the polypropylene surface so as to provide a coating rate, after drying, of 3 g/m 2 . This was followed by heating for 15 seconds in an oven at 180°C to obtain a sample (packaging material) according to Example 1-1. Example 1-2
    [00122] A sample (conditioning material) was prepared by proceeding as in Example 1-1, but changing the 500 g of the surface treatment agent to 300 g. The carbon content and the fluorine content of the obtained surface-modified fine silica particles (powder) are shown in Table 1. Example 1-3
    [00123] A sample was prepared proceeding as in Example 1-1, but changing the 500 g of the surface treatment agent to 800 g. The carbon content and fluorine content of the obtained surface-modified fine silica particles (powder) are shown in Table 1. Example 1-4
    [00124] A sample (packaging material) was prepared by proceeding as in Example 1-1, but changing the 500 g of the surface treatment agent to 25 g and using a silica fume powder having an average primary particle diameter of 30 nm and a BET specific surface area of 50 m2/g (product name: AEROSIL 50, from Nippon Aerosil Co., Ltd.) as the metal oxide particles. The carbon content and fluorine content of the obtained surface-modified fine silica particles (powder) are shown in Table 1. Example 1-5
    [00125] A sample (packaging material) was prepared proceeding as in Example 1-1, but using a silica fume powder having an average primary particle diameter of 30 nm and a BET specific surface area of 50 m2/ g (product name: AEROSIL 50, from Nippon Aerosil Co., Ltd.) as the metal oxide particles. The carbon content and the fluorine content of the obtained surface-modified fine silica particles (powder) are shown in Table 1. Example 1-6
    [00126] A sample (packaging material) was prepared by proceeding as in Example 1-1, but changing the 500 g of the surface treatment agent to 750 g and using a silica fume powder having an average primary particle diameter of 7 nm and a BET specific surface area of 300 m2/g (product name: AEROSIL 300, from Nippon Aerosil Co., Ltd.) as the metal oxide particles. The carbon content and fluorine content of the obtained surface-modified fine silica particles (powder) are shown in Table 1. Comparative Example 1-1
    [00127] A sample was prepared proceeding as in Example 1-1, but changing the 500 g of the surface treatment agent to 20 g. The carbon content and the fluorine content of the obtained surface-modified fine silica particles (powder) are shown in Table 1. Comparative Example 1-2
    [00128] A sample (packaging material) was prepared by proceeding as in Example 1-1, but using 100 g of trifluoropropyltrimethoxysilane as the treatment agent. The carbon content and fluorine content of the obtained surface-modified fine silica particles (powder) are shown in Table 1. Example 2-1
    [00129] A liquid dispersion was prepared according to "(2) Production of the liquid dispersion" of Example 1-1 by adding 30 parts by weight of the fine surface-modified silica particles and a commercially available heat-sealing agent ( 100 parts by weight of a liquid dispersion of thermosealing agent of the polypropylene type (solids content = 18% by weight, the same applies below.)) to 200 parts by weight of an organic solvent (toluene), with mixture. A sample (packaging material) was prepared by proceeding as in Example 1-1, but using the obtained liquid dispersion. Example 2-2
    [00130] A liquid dispersion was prepared according to "(2) Production of the liquid dispersion" of Example 1-2 by adding 30 parts by weight of the fine surface-modified silica particles and a commercially available heat-sealing agent ( 100 parts by weight of a liquid dispersion of a thermosealing agent of the polypropylene type) to 200 parts by weight of an organic solvent (toluene), with mixing. A sample (packaging material) was prepared by proceeding as in Example 1-2, but using the obtained liquid dispersion. Example 2-3
    [00131] A liquid dispersion was prepared in accordance with "(2) Production of the liquid dispersion" of Example 1-3 by adding 30 parts by weight of the fine surface-modified silica particles and a commercially available heat-sealing agent ( 100 parts by weight of a liquid dispersion of a thermosealing agent of the polypropylene type) to 200 parts by weight of an organic solvent (toluene), with mixing. A sample (packaging material) was prepared by proceeding as in Example 1-3, but using the obtained liquid dispersion. Example 2-4
    [00132] A liquid dispersion was prepared in accordance with "(2) Production of the liquid dispersion" of Example 1-4 by adding 30 parts by weight of the fine surface-modified silica particles and a commercially available heat-sealing agent ( 100 parts by weight of a liquid dispersion of a thermosealing agent of the polypropylene type) to 200 parts by weight of an organic solvent (toluene), with mixing. A sample (packaging material) was prepared by proceeding as in Example 1-4, but using the obtained liquid dispersion. Example 2-5
    [00133] A liquid dispersion was prepared according to "(2) Production of the liquid dispersion" of Example 1-5 by adding 30 parts by weight of the fine surface-modified silica particles and a commercially available heat-sealing agent ( 100 parts by weight of a liquid dispersion of a thermosealing agent of the polypropylene type) to 200 parts by weight of an organic solvent (toluene), with mixing. A sample (packaging material) was prepared by proceeding as in Example 1-5, but using the obtained liquid dispersion. Example 2-6
    [00134] A liquid dispersion was prepared according to "(2) Production of the liquid dispersion" of Example 1-6 by adding 30 parts by weight of the fine surface-modified silica particles and a commercially available heat-sealing agent ( 100 parts by weight of a liquid dispersion of a thermosealing agent of the polypropylene type) to 200 parts by weight of an organic solvent (toluene), with mixing. A sample (packaging material) was prepared by proceeding as in Example 1-6, but using the obtained liquid dispersion. Comparative Example 2-1
    [00135] A liquid dispersion was prepared according to "(2) Production of the liquid dispersion" of Comparative Example 1-1 by adding 30 parts by weight of the fine surface-modified silica particles and a heat sealing agent commercially available (100 parts by weight of a liquid dispersion of a thermosealing agent of the polypropylene type) to 200 parts by weight of an organic solvent (toluene), with mixing. A sample (packaging material) was prepared by proceeding as in Comparative Example 1-1, but using the obtained liquid dispersion. Comparative Example 2-2
    [00136] A liquid dispersion was prepared according to "(2) Production of the liquid dispersion" of Comparative Example 1-2 by adding 30 parts by weight of the fine surface-modified silica particles and a commercially available heat sealing agent (100 parts by weight of a liquid dispersion of a thermosealing agent of the polypropylene type) to 200 parts by weight of an organic solvent (toluene), with mixing. A sample (packaging material) was prepared by proceeding as in Comparative Example 1-2, but using the obtained liquid dispersion. Test Example 1 (Oil Repellent)
    [00137] The oil repellency (25°C) was verified for the samples prepared in the examples and in the comparative examples. Specifically, for each sample, the surface that had been treated with respect to water repellency and oil repellency was used as the test surface, and several drops of olive oil were dropped onto it and the state of the drops was observed. The commercial product AJINOMOTO Olive Oil (edible olive oil, viscosity = 0.9 dPa.s (20°C), from Ajinomoto Co., Inc.) was used as the olive oil. For the evaluation, an "O" was assigned when oil repellency was exhibited (rolled in the shape of a ball), while an "x" was assigned when oil repellency was not seen (it did not roll and wetting occurred). These results are given in Tables 1 and 2. Test Example 2 (Contact Angle)
    [00138] The contact angle (25°C) was measured for the samples obtained in the examples and comparative examples. Specifically, for each sample, the surface that had been treated for water repellency and oil repellency was used as the test surface, and the contact angles for pure water and olive oil (approximately 2 to 4 µL) were measured using a contact angle meter (the solid-liquid interface analyzer "DropMaster 300" from Kyowa Interface Science Co., Ltd.). For the measurement results, N = 5 and the mean value of these contact angles is given for the result. The commercial product "AJINOMOTO Olive Oil" (edible olive oil, from Ajinomoto Co., Inc.) was used as the olive oil. The results are given in Tables 1 and 2. Test Example 3 (Angle of Roll)
    [00139] The roll angle (25°C) was measured for the samples obtained in the examples and comparative examples. Specifically, for each sample, the surface that had been treated for water repellency and oil repellency was used as the test surface; this surface was secured, facing upwards, onto a flat horizontal bed, using a clamp; olive oil was dripped on it from a near bank; the horizontal flat bed was tilted; and the angle at which the olive oil began to flow was observed. The commercial product "AJINOMOTO Olive Oil" (edible olive oil, from Ajinomoto Co., Inc.) was used as the olive oil. The results are given in Tables 1 and 2. Test Example 4 (Wear resistance)
    [00140] Durability (wear resistance) was examined for the samples obtained in the examples and comparative examples. The test method here was based on the JIS standard, "JIS L 0849". Specifically, for each sample, the surface that had been treated for water repellency and oil repellency was used as the test surface; the wear test was carried out using a wear tester (Showa Juki Co., Ltd.); and the degree of conservation of oil repellency versus olive oil was then evaluated. The following conditions were used: a dry cloth was attached to the tip of the friction element and 100 back and forth rubbing excursions were performed on the test surface, under a load of 2 N, at a rate of 30 back excursions and forward per minute. The commercial product "AJINOMOTO Olive Oil" (edible olive oil, from Ajinomoto Co., Inc.) was used as the olive oil. For the evaluation, an "O" was assigned when an oil repellency was maintained at the same level as in Test Example 1, while an "x" was assigned when a loss of oil repellency occurred. These results are given in Tables 1 and 2. Test Example 5 (Thermal sealability test)
    [00141] The thermal sealing ability was examined for the samples obtained in Examples 2-1 to 2-6 and in Comparative Examples 2-1 and 2-2. Specifically, a lid was prepared by cutting a lid shape (90mm x 90mm square shape) from the particular packaging material sample, and a packaging was fabricated by heat sealing this lid onto a polypropylene container. with flange (molded to provide a flange width of 3.5 mm, a flange outer diameter of 75 mm x 68 mm inner diameter, a height of approximately 68 mm, and an inner volume of approximately 155 cm3). The thermal seal conditions were a flat type seal for 1.0 second at a temperature of 200°C and a pressure of 294.2 kPa (3 kgf/cm2). A flap in the lid on the sealed housing was pulled at a rate of 100 mm/minute in the direction of an elevation angle of 45°, as seen from the starting point for opening, and the maximum load (N) at the beginning of the opening was measured. The results are given in Table 2. [Table 1] (1st part)




    [00142] As is also clear from these results, the coating films of the examples, which contain composite particles containing metal oxide (fine surface-modified silica particles), covered in a coating amount determined by a coating layer comprising a poly(fluoroalkyl methacrylate) resin, may exhibit better water repellency and better oil repellency than the comparative examples.
    权利要求:
    Claims (11)
    [0001]
    1. Water and oil repellent coating film, which is formed on a surface of a substance to impart water repellency and oil repellency, characterized in that (1) the coating film comprises a particle composite containing metal oxide; (2) the composite particle comprises (a) a metal oxide particle and (b) a cover layer which contains a poly(fluoroalkyl methacrylate) resin and is formed on the surface of the metal oxide particle; (3) a value generated by dividing the fluorine content (% by weight) of the composite particle by a surface area (m 2 /g) of the metal oxide particle is 0.025 to 0.180; (4) an average primary particle diameter of the metal oxide particle is 5 to 50 nm; and (5) the coating film includes composite particles containing metal oxide and voids formed between those particles.
    [0002]
    2. Water and oil repellent coating film according to claim 1, characterized in that a value produced by dividing the carbon content (% by weight) of the composite particle by the surface area (m2/g) of the metal oxide particle is 0.05 to 0.400.
    [0003]
    3. Water and oil repellent coating film according to claim 1 or 2, characterized in that the metal oxide particle is at least a selection from silicon oxide particles, aluminum oxide particles , and titanium oxide particles.
    [0004]
    4. Water and oil repellent coating film according to any one of claims 1 to 3, characterized in that the covering layer does not contain a silicon component.
    [0005]
    5. Water and oil repellent coating film according to any one of claims 1 to 4, characterized in that the coating film is porous.
    [0006]
    6. Water and oil repellent coating film according to any one of claims 1 to 5, characterized in that the surface of the coating film forming the outermost surface has an irregular surface structure which is formed by the particle composite.
    [0007]
    7. Water and oil repellent coating film according to any one of claims 1 to 6, characterized in that the content of composite particle containing metal oxide in the coating film is 10 to 100% by weight.
    [0008]
    8. Water and oil repellent coating film according to any one of claims 1 to 7, characterized in that the coating film additionally contains an adhesive component.
    [0009]
    9. Packaging material, characterized in that it comprises the water and oil repellent coating film, as defined in any one of claims 1 to 8.
    [0010]
    10. Packaging material according to claim 9, characterized in that it comprises the water and oil repellent coating film as defined in any one of claims 1 to 8, a thermal sealing layer, and a layer of base material in the sequence indicated.
    [0011]
    11. Packaging material according to claim 10, characterized in that all or a part of the water and oil repellent coating film present on a region that undergoes heat sealing is incorporated in the heat sealing layer when the heat sealing is effected.
    类似技术:
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    同族专利:
    公开号 | 公开日
    PL2762537T3|2018-10-31|
    PT2762537T|2018-06-07|
    AU2013328136A1|2015-03-19|
    WO2014057712A1|2014-04-17|
    US20150247079A1|2015-09-03|
    EP2762537A4|2015-09-30|
    MX2015003806A|2015-09-29|
    AU2013328136B2|2017-01-05|
    EP2762537B1|2018-04-25|
    CA2887585C|2020-07-07|
    TR201808227T4|2018-07-23|
    TW201414822A|2014-04-16|
    CN103946322B|2016-04-20|
    KR20140065401A|2014-05-29|
    IN2015DN02880A|2015-09-11|
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    RU2015117782A|2016-11-27|
    CN103946322A|2014-07-23|
    RU2646931C2|2018-03-12|
    BR112014016192A8|2017-07-04|
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    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2018-03-27| B15K| Others concerning applications: alteration of classification|Ipc: C09D 7/00 (2018.01), C09C 1/28 (2006.01), C09C 1/3 |
    2019-08-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-06-01| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    2021-06-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-07-20| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/06/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2012227541A|JP5242841B1|2012-10-13|2012-10-13|Water- and oil-repellent coating films and articles containing the coating films|
    JP2012-227541|2012-10-13|
    PCT/JP2013/065864|WO2014057712A1|2012-10-13|2013-06-07|Water- and oil-repellent coating film and article containing same|
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