Slide film and container containing aqueous emulsion

Abstract

To provide a slide film that exhibits slide durability with respect to aqueous emulsions such as emulsions, and a storage container for aqueous emulsions using the slide film.SOLUTION: The slide film of the present invention is formed on a surface of a substrate and contains (A) a cured product of a moisture-curable silicone oligomer, (B) a curing catalyst for moisture curing, and (C) a dimethyl silicone oil having a kinematic viscosity of 500 to 500,000 mm2 / s at 25°C, wherein the blending amount of the component (C) is 500 to 800 pts.mass relative to a total of 100 pts.mass of the components (A) and (B). The slide film enables sliding of an aqueous emulsion.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a sliding membrane that slides off an aqueous emulsion, and also to a container containing an aqueous emulsion that utilizes such a sliding membrane. [Background technology]

[0002] In a storage container containing an aqueous emulsion, it is desired to form a coating film that exhibits sliding properties that allow the contents to slide down quickly inside a tilted container so that the user can quickly empty the contents and use them up to the last drop without leaving any residue in the container.

[0003] As a water-repellent film, there is one intended to prevent the adhesion of water stains to the surface of a vehicle body, for example. Patent Document 1 discloses a composition for forming a film to impart water-repellent properties to metal or resin surfaces, which contains a hydrolyzable group-containing silicone oligomer (also called a moisture-curable silicone oligomer), a reactive silicone oil, a hydrolysis catalyst, and an organic solvent. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2019-022093 Summary of the Invention [Problem to be solved by the invention]

[0005] Generally, substances with relatively high surface free energy, such as water (72 mJ / m 2 (25°C)) easily slides on the surface of materials with low surface free energy, such as oil. However, simply being water-repellent is not enough; in practical terms, it is important that the material repeatedly demonstrates water-repellency and that this is maintained for a long time on the surface of the substrate, in other words, that it has "water-repellent durability."

[0006] The coating composition of Patent Document 1 contains a reactive silicone oil, which refers to an oil having a reactive functional group such as a carbinol group bonded to one end of a silicone chain. The reactive functional group can interact with a substrate such as a metal, and one end of the silicone chain is adsorbed to the substrate, thereby improving the durability of the film (see paragraph 0053 of Patent Document 1).

[0007] On the other hand, the inventors have found that aqueous emulsions (e.g., emulsions, liquid foundations, inks, etc.) have a surface free energy lower than that of water. Surface free energy: 24 to 33 mJ / m 2 We have been searching for a film that exhibits "slip-off durability" against a temperature of 25°C. However, films containing reactive silicone oils such as those described in Patent Document 1 may not be able to achieve the desired slide-off durability against aqueous emulsions that have a surface free energy lower than that of water. In addition, reactive silicone oils are often expensive, which is a cost disadvantage.

[0008] The present invention has been made in consideration of the above problems, and aims to provide a sliding membrane that exhibits sliding resistance against aqueous emulsions such as lotions, and a container containing an aqueous emulsion that utilizes such a sliding membrane. [Means for solving the problem]

[0009] The inventors conducted various tests and found that a film containing non-reactive dimethyl silicone oil, which does not have reactive functional groups, exhibits slide-off resistance against aqueous emulsions. The surface free energy of dimethyl silicone oil is 21 mJ / m 2 (25°C), which is smaller than the surface free energy of the target aqueous emulsion, so the aqueous emulsion easily slides on the surface of the dimethyl silicone oil formed on the film surface. 2 By using dimethyl silicone oil with a viscosity of 1 / s (25°C), a sliding film exhibiting the desired sliding durability against aqueous emulsions was obtained, leading to the completion of the present invention.

[0010] That is, the sliding film of the present invention is formed on the surface of a substrate, (A) a cured product of a moisture-curable silicone oligomer; (B) a curing catalyst for moisture curing, and (C) Kinematic viscosity at 25°C is 500 to 500,000 mm 2 / s, containing dimethyl silicone oil, The blending amount of component (C) is 500 to 800 parts by mass per 100 parts by mass of the total of components (A) and (B), and is characterized by allowing the aqueous emulsion to slide off.

[0011] The sliding film of the present invention is formed on the surface of a substrate, (A) a cured product of a moisture-curable silicone oligomer; (B) a curing catalyst for moisture curing, and (C) dimethyl silicone oil, Component (C) has a kinematic viscosity of 500,000 to 500,000 mm at 25°C. 2 A mixture of two or more dimethyl silicone oils having kinematic viscosities selected from the group consisting of dimethyl silicone oils having kinematic viscosities of 1.5 million to 400,000 mm / s. 2 / s, The blending amount of component (C) is 500 to 800 parts by mass per 100 parts by mass of the total of components (A) and (B), and is characterized by allowing the aqueous emulsion to slide off.

[0012] Alternatively, the sliding film of the present invention is formed on the surface of a substrate, (A) a cured product of a moisture-curable silicone oligomer; (B) a curing catalyst for moisture curing; (C) Kinematic viscosity at 25°C is 500 to 500,000 mm 2 / s dimethyl silicone oil, and (D) Kinematic viscosity at 25°C is 50 mm 2 / s or more, 500mm 2 / s, containing one or more dimethyl silicone oils selected from the group consisting of dimethyl silicone oils having a kinematic viscosity of less than the combined amount of the (C) component and the (D) component is 500 to 800 parts by mass per 100 parts by mass of the combined amount of the (A) component and the (B) component; The kinematic viscosity of the dimethyl silicone oil, which is a mixture of components (C) and (D), is 1.5 to 200,000 mm 2 / s range and is characterized by the ability to slide off aqueous emulsions.

[0013] In the container containing the aqueous emulsion of the present invention, the sliding film is formed on the inner surface of the storage container, and the surface free energy of the aqueous emulsion is 24 to 33 mJ / m 2 It is characterized in that: The mass per area of ​​the sliding film is 10 to 65 g / m 2 It is preferable that: [Effects of the Invention]

[0014] According to the present invention, the sliding film formed on the surface of the substrate does not contain reactive silicone oil and has a kinematic viscosity of 500 to 500,000 mm at 25 ° C. 2 By including a non-reactive dimethyl silicone oil with a surface free energy of 24-33 mJ / m at 25°C, the dimethyl silicone oil on the membrane surface can be used to form an aqueous emulsion. 2 Furthermore, since the sliding film contains a cured product of the moisture-curable silicone oligomer, the cured product of the silicone oligomer firmly holds the dimethyl silicone oil, and the sliding property against the aqueous emulsion is maintained for a long time. [Brief explanation of the drawings]

[0015] [Figure 1] 1 is a schematic diagram of the structure of the sliding film of the present invention formed on a substrate. [Figure 2] 1 is an image showing the shape of a PET container used in an example. [Figure 3] 1 is a distribution diagram of the properties of an aqueous emulsion (horizontal axis: surface free energy, vertical axis: viscosity). [Figure 4]This image serves as a criterion for determining whether emulsion has slipped off inside a PET container. [Figure 5] 1 shows micrographs of films formed on slide glasses in Examples and Comparative Examples, observed at 200x (or 2000x). DETAILED DESCRIPTION OF THE INVENTION

[0016] The following describes embodiments of the present invention, but these are representative examples of embodiments of the present invention, and the present invention is not limited to these details as long as it does not exceed the gist of the present invention. In the following description, "parts" means "parts by mass" and "%" means "% by mass" unless otherwise specified. Furthermore, unless otherwise specified, "silicone oligomer" and "silicone oil" in the description refer to "moisture-curing silicone oligomer" and "dimethyl silicone oil". Here, an embodiment in which a sliding film is formed inside a storage container will be described, but the sliding film of the present invention can be formed on the surface of various items, not limited to storage containers.

[0017] <Storage container with sliding membrane> The article having a sliding film of this embodiment is suitable for use with aqueous emulsions (e.g., emulsions, liquid foundations, inks, etc.) having a surface free energy lower than that of water. In particular, the surface free energy at 25°C is 24 to 33 mJ / m 2 The container is made of glass or resin depending on the application. Specific applications include storing various cosmetics, detergents, food products, etc. Figure 1 is a schematic representation of the sliding film formed inside such a storage container. Referring to Figure 1, the inner surface of the container (substrate 1) that comes into contact with the aqueous emulsion 20 contains a cured product 12 of a moisture-curable silicone oligomer, a curing catalyst 14 for moisture curing, and a silicone oil having a kinetic viscosity of 500 to 500,000 mm at 25°C. 2The sliding film 10 is formed by containing dimethyl silicone oil 16, which is a dimethyl silicone oil having a molecular weight of 1 / s, and the amount of dimethyl silicone oil is 500 to 800 parts by mass per 100 parts by mass of the total of the cured product of the moisture-curable silicone oligomer and the curing catalyst for moisture curing. The dimethyl silicone oil 16 is exposed on the surface of the sliding film 10, and the sliding film 10 exhibits sliding properties against the aqueous emulsion 20.

[0018] Aqueous emulsions are oil-in-water (O / W) emulsions, and typical examples include cosmetic lotions such as emulsions, liquid detergents, water-based glues, edible sauces and ketchups, etc. The viscosity of aqueous emulsions is in the range of 120 to 17,000 mPa·s, particularly 2,000 to 17,000 mPa·s, when measured for 300 seconds using a B-type viscometer with an L4 spindle at the desired rotation speed (30 rpm) and a temperature of 25°C.

[0019] In addition, the surface free energy of the aqueous emulsion is 18 to 25 mJ / m 2 The polar component is in the range of 0.3 to 10 mJ / m 2 The total value (dispersive component and polar component) is within the range of 24 to 33 mJ / m 2 In particular, the total value shall be within the range of 27 to 33 mJ / m 2 It shall be within the range of.

[0020] <Paint> The paint used to form the sliding film is prepared by mixing a moisture-curing silicone oligomer, a moisture-curing catalyst, and dimethyl silicone oil. The moisture-curing silicone oligomer has a relatively low molecular weight (less than 1,000) and is liquid, so it acts as a solvent, eliminating the need to mix a solvent into the paint. However, when spraying, it is possible to add a solvent and dilute the paint by about two times.

[0021] (Moisture-curing silicone oligomer) Moisture-curable silicone oligomers refer to polymers with low molecular weight among silicone resins, and are broadly classified according to the presence or absence of alkoxysilyl groups and reactive functional groups (epoxy, methacryl, mercapto, etc.). In this embodiment, a moisture-curable silicone oligomer having an alkoxysilyl group but no reactive functional group is used. Specifically, the moisture-curable silicone oligomer is an alkoxysilane compound represented by formula (1) or a partial hydrolysis condensate thereof. R 1 x -Si(OR 2 ) 4-x ···(1) In the above formula (1), R 1 represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and R 2 represents an alkyl group, and x is an integer of 0 to 3, preferably 1 or 2. R 1 In the above, examples of the unsubstituted monovalent hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

[0022] Examples of alkyl groups include alkyl groups having 1 to 18 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, hexyl, heptyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, isodecyl, dodecyl, tetradecyl, hexadecyl, and octadecyl. Examples of cycloalkyl groups include cycloalkyl groups having 3 to 8 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of aryl groups include aryl groups having 6 to 8 carbon atoms, such as phenyl, tolyl, and xylyl. Examples of aralkyl groups include aralkyl groups having 7 or 8 carbon atoms, such as benzyl, 1-phenylethyl, 2-phenylethyl, and o-, m-, or p-methylbenzyl.

[0023] R 1In the formula, examples of the substituted monovalent hydrocarbon group include those in which the hydrogen atoms of the above-mentioned unsubstituted monovalent hydrocarbon groups have been substituted with substituents, and examples of such substituents include halogen atoms (e.g., chlorine, fluorine, bromine, and iodine), hydroxyl, cyano, amino, and carboxyl. These substituents may be the same or different, and may be present in a number of 1 to 3. R 1 Among these, hydrogen, an alkyl group having 1 to 18 carbon atoms, and an aryl group having 6 to 8 carbon atoms are preferred. 2 In the formula (R), examples of the alkyl group include alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl. 1 and R 2 are each independently and may be the same or different from each other.

[0024] Specific examples of the alkoxysilane compound include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, and mixtures thereof.

[0025] The partial hydrolysis condensate of the alkoxysilane compound is obtained by adding water to the above-mentioned alkoxysilane compound and raising the temperature while stirring in the presence of a known catalyst, thereby causing partial hydrolysis and condensation. The moisture-curable silicone oligomer has a kinematic viscosity at 25°C of, for example, 0.1 to 500 mm 2 / s, preferably 0.5 to 250 mm 2 / s.

[0026] Moisture-curable silicone oligomers are commercially available, such as XR31-B1410 (manufactured by Momentive Performance Materials Japan, LLC), MSE100 (manufactured by Wacker Asahi Kasei Silicones), and KR-500 (manufactured by Shin-Etsu Chemical Co., Ltd.) These moisture-curable silicone oligomers may be used alone or in combination of two or more.

[0027] Because the moisture-curing silicone oligomers described above contain alkoxysilyl groups (Si-OR), adding a curing catalyst promotes hydrolysis and dealcoholization condensation reactions, causing them to react with moisture in the air and cure at room temperature, forming a hard coating with a three-dimensional network structure. For example, a compound having methyl in the organic substituent and methoxy in the alkoxy group, with a kinematic viscosity of 20 to 30 mm at 25°C 2 When using a two-component moisture-curing silicone oligomer such as , it is recommended to add a titanium-based or aluminum-based curing catalyst at 1 to 15 wt %. Aluminum-based curing catalysts are preferred because they can form high-hardness coatings. Alternatively, a one-component moisture-curing silicone oligomer containing a curing catalyst may be used.

[0028] (Moisture curing catalyst) The curing catalyst is not limited as long as it is a catalyst that can cure the moisture-curable silicone oligomer, and examples thereof include organic tin compounds such as dibutyltin diacetate, dibutyltin dioctylate, and dibutyltin dilaurate; organic aluminum compounds such as aluminum tris(acetylacetone), aluminum tris(ethyl acetoacetate), and aluminum diisopropoxy(ethyl acetoacetate); and organic aluminum compounds such as zirconium(acetylacetone), zirconium tris(acetylacetone), zirconium tetrakis(ethylene glycol monomethyl ether), zirconium tetrakis(ethylene glycol monoethyl ether), and zirconium tetrakis(ethylene glycol monobutyl ether). Examples of suitable organic compounds include organic zirconium compounds such as titanium tetrakis(ethylene glycol monomethyl ether), titanium tetrakis(ethylene glycol monoethyl ether), and titanium tetrakis(ethylene glycol monobutyl ether); organic titanium compounds such as titanium tetrakis(ethylene glycol monobutyl ether); acids such as mineral acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, and organic acids such as formic acid, acetic acid, oxalic acid, and trifluoroacetic acid; alkalis such as inorganic bases such as ammonia, sodium hydroxide, and potassium hydroxide, and organic bases such as ethylenediamine and alkanolamine; and amino compounds such as amino-modified silicones, aminosilanes, silazanes, and amines. Of these, preferred are organic tin compounds, organic aluminum compounds, organic titanium compounds, mineral acids, and amino compounds.

[0029] Curing catalysts are commercially available, such as CR15 (manufactured by Momentive Performance Materials Japan, LLC), D-20, DX-175, and DX-9740 (all manufactured by Shin-Etsu Chemical Co., Ltd.). These curing catalysts may be used alone or in combination of two or more. The blending ratio of the curing catalyst is, for example, 0.1 to 70% by weight, preferably 1 to 50% by weight, and more preferably 2 to 30% by weight, based on the total amount of the moisture-curable silicone oligomer. If the blending ratio of the curing catalyst is within the above range, the curing reaction can proceed sufficiently.

[0030] (Dimethyl silicone oil) The dimethyl silicone oil is not particularly limited as long as it has a straight-type dimethylpolysiloxane structure and bleeds out onto the film surface, and one type may be used alone or two or more types may be used in combination. Dimethyl silicone oil is represented by the general formula (1).

[0031] [ka]

[0032] In the general formula (1), n ​​represents an integer of 0 to 2000. The relationship between the kinematic viscosity and molecular weight of dimethyl silicone oil is as follows: Kinematic viscosity (cSt=mm 2 / s) molecular weight ------------------------------------------------------------------ 30 50 50 65 100 6,610 200 11,188 500 19,079 1,000 26,439 3,000 40,559 10,000 59,488 30,000 79,915 100,000 105,757 300,000 132,491 500,000 145,947 ------------------------------------------------------------------

[0033] Specific examples of dimethyl silicone oils include dimethyl silicone oils manufactured by Momentive Performance Materials Japan LLC (e.g., the TSF451 series, TSF400, TSF401, and THF450 series), dimethyl silicone oils manufactured by Shin-Etsu Chemical Co., Ltd. (e.g., the KF96 series, KF96L series, KF96A series, KF96H series, KF69 series, KF965, and KF968), dimethyl silicone oils manufactured by Dow Corning Toray Co., Ltd. (e.g., the SH200 series), and dimethyl silicone oils manufactured by Wacker Asahi Kasei Silicones (e.g., the AK series, AKF series, and AKC series).

[0034] (Dimethyl silicone oil with relatively high viscosity) In particular, the kinematic viscosity at 25°C is 500 to 500,000 mm 2 Dimethyl silicone oils with a relatively high viscosity in the range of 5,000 to 100,000 mm / s are preferred, and particularly those with a viscosity in the range of 5,000 to 100,000 mm / s. 2 It is preferable that the range is / s.

[0035] Dimethyl silicone oil forms an oil layer on the surface of the sliding film, enhancing the sliding properties of the aqueous emulsion that comes into contact with it. Therefore, it is preferable that the surface free energy of the oil itself is smaller than the surface free energy of the aqueous emulsion. The surface free energy of dimethyl silicone oil is 21.0 to 23.0 mJ / m 2 When the thickness is within the range, the sliding properties of the sliding film are particularly effectively exhibited.

[0036] The amount of dimethyl silicone oil to be added should be within the range of 500 to 800 parts by mass per 100 parts by mass of the moisture-curable silicone oligomer and curing catalyst combined. If the amount of dimethyl silicone oil is too low, good sliding properties may not be achieved on the inner surface of the container. Furthermore, because the silicone oligomer acts as a solvent, adding too much silicone oil may make it difficult to create a paint, impair the formability of the coating, or adversely affect the container properties.

[0037] Dimethyl silicone oil is highly compatible with moisture-curable silicone oligomers and blends well with the surface of the cured moisture-curable silicone oligomer attached to the substrate surface. This allows the dimethyl silicone oil to spread thinly on the surface of the cured silicone oligomer (three-dimensional network structure), forming a layer of dimethyl silicone oil on the surface of the sliding film. When the sliding film is applied to an article in this way, a layer of dimethyl silicone oil is formed on the surface of the sliding film, exhibiting excellent sliding properties against aqueous emulsions. In other words, when the aqueous emulsion comes into contact with the dimethyl silicone oil on the surface of the sliding film, the difference in surface tension with the dimethyl silicone oil causes it to easily slide off the film surface. Furthermore, since the dimethyl silicone oil blends well with the surface of the cured moisture-curable silicone oligomer, it is held by the surface, making it less likely to fall off the substrate surface, and maintaining its sliding properties for a long time.

[0038] Furthermore, if we are simply considering sliding the aqueous emulsion down, it is better for the viscosity of the silicone oil on the surface of the coating to be low. This is because the easier it is for the silicone chains of the silicone oil on the surface of the coating to rotate (roll) around their axes, the easier it is for the aqueous emulsion that comes into contact with it to roll. However, when the viscosity of the aqueous emulsion is high, for example, 120 to 17,000 mPa·s, if the viscosity of the silicone oil is low, there is a problem that when the aqueous emulsion slides down, the silicone oil is easily removed (falls off) along with it. Therefore, in this embodiment, a relatively viscous dimethyl silicone oil is used, particularly one with a kinematic viscosity at 25°C of 500 to 500,000 mm 2 By including dimethyl silicone oil in the range of / s, it is possible to prevent the adhesive from dropping off together with the aqueous emulsion. Furthermore, the low molecular weight silicone oligomer acts as a solvent in the coating, making it easier for the relatively viscous dimethyl silicone oil to form a uniform film on the surface of the substrate. For example, 0.65 to 1 million mm 2When several dozen types of dimethyl silicone oils with standard viscosities in the kinematic viscosity range are available, it is possible to create a dimethyl silicone oil with the desired viscosity by mixing two or more types of standard viscosities. In this embodiment, a dimethyl silicone oil with a kinematic viscosity of two or more types can be used.

[0039] (Including a mixture of dimethyl silicone oils with different dynamic viscosities) For example, the kinematic viscosity at 25°C is 500,000 to 500,000 mm 2 At least two types of dimethyl silicone oils having predetermined kinematic viscosities are selected from a group of dimethyl silicone oils having kinematic viscosities in the range of 1.5 to 400,000 mm / s. These are then mixed at a predetermined blending ratio to obtain a mixture having a kinematic viscosity of 1.5 to 400,000 mm / s. 2 Dimethyl silicone oil having a viscosity within the range of / s is obtained. The dimethyl silicone oil obtained in this manner can be used in the paint of this embodiment.

[0040] (Contains both relatively high viscosity dimethyl silicone oil and relatively low viscosity dimethyl silicone oil) For example, the kinematic viscosity at 25°C is 500 to 500,000 mm 2 At least one dimethyl silicone oil having a predetermined kinematic viscosity is selected from a group of dimethyl silicone oils having a kinematic viscosity in the range of 50 mm / s. 2 / s or more, 500mm 2 At least one type of dimethyl silicone oil having a predetermined kinematic viscosity is selected from a group of dimethyl silicone oils having a kinematic viscosity of less than 1 / s. These are then mixed at a predetermined blending ratio to produce a mixture having a kinematic viscosity of 1.5 to 200,000 mm. 2 Dimethyl silicone oil having a viscosity within the range of / s is obtained. The dimethyl silicone oil obtained in this manner can be used in the paint of this embodiment.

[0041] For example, if the kinematic viscosity is 1,000 mm 2When using a dimethyl silicone oil having a molecular weight of 26,439, one type of dimethyl silicone oil having a molecular weight of 26,439 can be selected. Or, the kinematic viscosity is 10,000 mm 2 / s and dimethyl silicone oil (molecular weight: 59,488) with a kinematic viscosity of 100 mm 2 When two types of silicone oil (molecular weight: 6,610) with a viscosity of 1,000 mm / s are mixed at a 1:1 ratio, the kinematic viscosity after mixing is 1,000 mm 2 / s, so such a mixture can be selected. The relationship between the mixing ratio and kinematic viscosity of two types of dimethyl silicone oil with different kinematic viscosities is shown below. Mixing ratio Dynamic viscosity after mixing ------------------------------------------------------------------ (10,000 mm 2 / s) (100mm 2 / s) 100% 0% 10000mm 2 / s 75% 25% 3000mm 2 / s 50% 50% 1000mm 2 / s 25% 75% 300mm 2 / s 0% 100% 100mm 2 / s ------------------------------------------------------------------

[0042] The combined blending amount of the dimethyl silicone oil selected from the higher viscosity group and the dimethyl silicone oil selected from the lower viscosity group is set to be within the range of 500 to 800 parts by mass per 100 parts by mass of the total of the silicone oligomer and curing catalyst. The dynamic viscosity of dimethyl silicone oil is 250mm 2If the viscosity is greater than / s, the polysiloxane main chains tend to become entangled, slowing down the movement (rolling, etc.) of the silicone oil. In this embodiment, it is advisable to mix a relatively low-viscosity dimethyl silicone oil with a relatively high-viscosity dimethyl silicone oil so that it acts as a solvent. This reduces the viscosity of the relatively high-viscosity dimethyl silicone oil, making it easier to move, and further improving the sliding properties of the aqueous emulsion.

[0043] In addition to the above components, the paint of this embodiment may contain various known additives, such as plasticizers, dispersants, antioxidants, UV absorbers, fillers, and leveling agents (to prevent repelling during spray painting), depending on the intended use of the container. Furthermore, for applications that do not require transparency, colorants such as pigments and dyes may also be added. Furthermore, crystalline additives (inorganic oxides such as titanium oxide and various waxes) may also be added. However, the amount of such additives to be added should be small enough so that the amount of dimethyl silicone oil in the paint is maintained within the aforementioned range, the formability of the coating film is not impaired, and the sliding properties of the coating film on the inner surface of the container are not impaired.

[0044] The coating material prepared with the above blending amounts is applied to the surface of the substrate in the container by spraying or flow coating. The mass of the coating material per area of ​​the substrate surface (amount of coating) can be freely changed depending on the application and is not limited, but is generally 10 to 65 g / m 2 If the amount of coating is too small, the sliding properties may decrease, or the coating may be worn away over long periods of use due to its thinness. Conversely, if the amount of coating is too large, the coating may become too thick for the number of years of actual use, which may not be economical. A more preferable amount of coating is 30 to 50 g / m 2 is.

[0045] The substrate to which the coating material of this embodiment is applied can be glass, resin, etc. Examples of resin that can be used include polyethylene terephthalate resin, acrylic resin, and polycarbonate resin. Specifically, the coating material can be applied to the surface of the substrate by any conventional coating method such as doctor blade, bar coating, dipping, air spray, roller brush, roller coater, etc. As for the drying method, in addition to drying by heating, the substrate to which the coating material has been applied can also be left in an atmosphere at about room temperature to form a sliding film. [Example]

[0046] The present invention will be described in more detail below based on examples, but the present invention is not limited to the contents of these examples.

[0047] Physical properties, etc. are measured by the following methods unless otherwise specified. [Amount] When determining the blending amount of a certain component, for example, the blending amount of dimethyl silicone oil, per 100 parts by mass of other components (for example, silicone oligomer and curing catalyst), if these components contain volatile components such as solvents, the blending amount is determined based on the amount of non-volatile components.

[0048] [Amount of application] The coating amount is the weight of the coating film after coating and drying per coated area, and is a calculated value. The amount of coating film used (g) after coating and drying is calculated from the difference in the container weight before coating and after coating and drying. This is divided by the coating area in the container to obtain the coating amount (g / m 2 ) Details of the coating area inside the container will be described later.

[0049] [Surface free energy] The surface free energy of aqueous emulsions is calculated based on the typical Kaelble and Uy theoretical formula. First, a film of the aqueous emulsion is formed on a glass slide, and the contact angles of 10 μL droplets of two reagents (e.g., diiodomethane and n-hexadecane, or water and formamide) on the film are measured using a contact angle meter, Drop Master DMs-401 (Kyowa Interface Science Co., Ltd.). These contact angle measurements are applied to the theoretical formula to calculate the dispersive and polar components of the surface free energy, and the sum of these is the surface free energy of the aqueous emulsion. The surface free energy of dimethylsilicone oil can be obtained in a similar manner, using water and diiodomethane as the reagents.

[0050] [viscosity] Regarding the viscosity of the aqueous emulsion, since the viscosity of "mayonnaise" according to literature is 8000 mPa·s, the viscosity of "Kewpie Half (registered trademark)" was measured using a Brookfield viscometer at various rotation speed settings to confirm the rotation speed conditions under which a viscosity value equivalent to the literature value was obtained, and an actual measured value of 7670 mPa·s was obtained at 30 rpm. Based on this, the rotation speed condition for measuring the viscosity of the aqueous emulsion was set to 30 rpm. To measure the viscosity of the aqueous emulsion, a 20 g vial (SV-50A) (manufactured by Nichiden Rika Glass Co., Ltd.) was used, and an L4 spindle (diameter 3.2 mm) was placed at the center of the vial's inner diameter of 26.5 mm, leaving a gap of 11.65 mm between the spindle and the inner wall of the vial.

[0051] The containers (substrates), test membranes, and contents (aqueous emulsions) used in the examples and comparative examples are as follows:

[0052] <Container> The container is made of polyethylene terephthalate (PET) as shown in Figure 2. The coating area of ​​the PET container is calculated by simply adding up the areas of the bottom and sides, assuming the inside of the container to be cylindrical (inner diameter 36.72 mm, height 102.5 mm) (1.29 × 10 -2 m 2 ) is used.

[0053] <Test membrane> (1) Moisture-curing silicone oligomer (methyl type, viscosity at 25°C: 1.2 mPa·s) (2) Moisture-curing catalyst (aluminum-based) (3) Dimethyl silicone oil (kinematic viscosity at 25°C of 10,000 cSt, 3,000 cSt, 1,000 cSt, 500 cSt, 350 cSt, 200 cSt, 100 cSt, 50 cSt, or 30 cSt) (4) Reactive silicone oil Dynamic viscosity: 2,000 cSt, side chain carboxyl modified Kinematic viscosity: 500cSt, one-terminal diol modified (5) Silicone resin (including solvent) Viscosity: 400mPa·s Viscosity: 18 mPa·s (methyl type) Kinematic viscosity: 85cSt (methyl / phenyl type)

[0054] The test film was formed by mixing the components used in the examples and comparative examples from the above ingredients in the prescribed amounts, stirring to prepare a coating, and then uniformly applying the specified amount to the inner surface of the container and drying. The coating method for the inner surface of the PET container was "spray" or "flow coating." After coating, in either coating method, the coating was dried at room temperature at 25°C to form a coating film.

[0055] In Example 1, a moisture-curable silicone oligomer, a moisture-curing catalyst, and dimethyl silicone oil (10,000 cSt) were used, and the amount of dimethyl silicone oil was set to 700 parts by mass per 100 parts by mass of the total of the silicone oligomer and the curing catalyst to obtain a test film. For the test films of Examples 2 to 4, dimethyl silicone oils with lower viscosities (3,000, 1,000, and 500 cSt) than in Example 1 were used, and the other conditions were the same as in Example 1.

[0056] In Example 5, a moisture-curable silicone oligomer, a moisture-curing catalyst, dimethyl silicone oil (10,000 cSt), and dimethyl silicone oil (100 cSt) were used, and the amount of dimethyl silicone oil (10,000 cSt) was 350 parts by mass per 100 parts by mass of the silicone oligomer and the curing catalyst, and the amount of dimethyl silicone oil (100 cSt) was 350 parts by mass per 100 parts by mass of the silicone oligomer and the curing catalyst, to obtain a test film.

[0057] Other components used in the comparative examples and their respective blending amounts are shown in Tables 1 to 4.

[0058] The test film was subjected to a slide-off durability (durability of removal performance) test using aqueous emulsions (emulsions 1 to 7, liquid foundation, and ink). Figure 3 shows the distribution of physical properties (surface free energy and viscosity) of the commercially available aqueous emulsions used in the test.

[0059] As described below, the test films of Examples 1 to 5 have a surface free energy of 24 to 33 mJ / m 2 It exhibits excellent slip resistance against aqueous emulsions with a viscosity of 120 to 17,000 mPa·s.

[0060] [Slip-down durability test] A container with a test film is filled with commercially available aqueous emulsion (10g of emulsion, 5g of liquid foundation, 10g of ink), and the inner stopper and cap are then put back on to seal the container. The container is then turned upside down and upright repeatedly as follows, and the sliding properties (removal performance) of the coating film against the aqueous emulsion are visually evaluated after each inversion. 1st time: upright → inverted (record the date and time of inversion: start date and time of 1st time) After the first inversion, leave the container in the inverted position until the aqueous emulsion no longer adheres to the inside surface (bottom and sides) of the container and it can be determined that the aqueous emulsion has slid down to the cap side. Once it can be visually confirmed that the aqueous emulsion has slid down, begin the second inversion. Second time: Inverted → Upright (record the date and time when it was upright: start date and time of the second time) Leave the container in the upright position until the aqueous emulsion no longer adheres to the inside surface (shoulder and sides) of the container and it can be determined that the aqueous emulsion has slid to the bottom. When it is visually confirmed that the aqueous emulsion has slid down, begin the third inversion. 3rd time (and every odd number of times thereafter): upright → inverted (same as the 1st time) 4th time (and every even number of times thereafter): Inverted → Upright (same as 2nd time)

[0061] The sliding properties of the inner surface of a container (whether it adheres easily or not) are affected not only by differences in the material of the inner surface of the container, but also by differences in the shape of the container (for example, the shape of the shoulder part, the shape of the bottom, etc.) (see the shape of a PET container in Figure 2).

[0062] The criteria for visually checking whether the aqueous emulsion has slid off will be explained using the images in Figure 4. The upper left of Figure 4 is a photograph of the PET container in Example 1 (Emulsion 1) before the 200th inversion, and is an image that can be used as a guide for determining whether the aqueous emulsion has "slid off." The upper right of Figure 4 is a photograph of the PET container in Comparative Example 13 (Emulsion 1, no coating) five days after the first inversion, and is an image that can be used as a guide for determining whether the aqueous emulsion has "not slid off." Similarly, the bottom left of Figure 4 is a photograph of Example 1 (lotion 5) taken before the 200th inversion, which serves as a guide for determining whether "sliding down." The bottom center of Figure 4 is a photograph of Comparative Example 34 (lotion 5, silicone oil only) taken 45 days after the first inversion, which serves as a guide for determining whether "sliding down." The bottom right of Figure 4 is a photograph of Comparative Example 35 (lotion 5, silicone oil only) taken 46 days after the first inversion, which also serves as a guide for determining whether "sliding down." These images are used as a guide to determine whether or not each aqueous emulsion has slipped off.

[0063] "Evaluation method for slip resistance" We will explain how to evaluate how long a container can maintain the ability of an aqueous emulsion to slide off (slide durability). First, we will explain the usage pattern of a commercially available emulsion (packaged in a 60 mL container). Assuming that the amount used per use is an amount that covers an area about the size of a 100 yen coin (approximately 2.5 mL per use), one commercially available emulsion can be used 24 times. In other words, if the emulsion's ability to slide off is maintained after the 24th use, the container's appearance (transparency) will be well maintained, and the emulsion container can be evaluated as having slide durability. The action of using a commercially available lotion in one go is to lift the container from the upright position, tilt it (to dispense the lotion), and then return it to the upright position, which is an action of "upright → inverted → upright." Therefore, repeating the inversion process in the above test up to 48 times corresponds to the number of uses (24 times) of one commercially available lotion. Therefore, the inversion process was repeated twice as many times, up to 100 times, and if there was no emulsion remaining on the inner surface of the container by the start of the 100th inversion and the emulsion was visually confirmed to have slid off, it could be determined that "slide-off durability (durability of emulsion removal) was present." After the 100th inversion, the evaluation of slide-off durability was continued until the start of the 200th inversion, which is twice as many, and the evaluation was terminated at the same time.

[0064] In the slide-down durability test, we used the "number of times per 12 hours (including holidays)" to properly evaluate the slide-down durability of aqueous emulsions, taking into account the slide-down speed of the aqueous emulsion. It is generally assumed that commercially available emulsions are used twice a day (every 12 hours). Therefore, it is desirable that after inverting the container, at most 12 hours later, there should be almost no emulsion remaining on the inner surface of the container, and that the slide-down of the emulsion can be visually confirmed. In other words, in the above slide-down durability test, if the number of inversions per 12 hours is 1 or more, the slide-down durability rating is high. Therefore, we decided to introduce the "number of times per 12 hours" as a numerical value to indicate the degree of slide-down durability. However, considering that emulsions are often left unused on holidays, the criterion for determining whether slide-down durability exists is 0.71 times per 12 hours (including holidays) or more (≒ 1 time × 5 days / 7 days). For example, if the reversal operation has reached its 200th time (reversal count: 199 times) and 54 days have passed since then, the number of times per 12 hours (including holidays) is calculated as 199 times / (54 days x 2) = 1.84 times.

[0065] After inversion, the container was left standing until it was determined that the aqueous emulsion had slid off. If the aqueous emulsion continued to adhere, the evaluation was terminated after a certain period of time had passed. In this case, the number of inversions per 12 hours was calculated from the number of inversions at the last inversion and the number of days elapsed. For example, if the number of inversions at the last inversion was 37 and 28 days had elapsed, the number of inversions per 12 hours (including holidays) would be calculated as 37 times / (28 days x 2) = 0.66 times.

[0066] The degree of slip resistance was evaluated according to the following criteria: If the number of inversions per 12 hours (including holidays) was 0.71 or more (rating A to B), there was no practical problem. A: Number of times per 12 hours (including holidays) is 1.0 or more B: Number of times per 12 hours (including holidays) is 0.71 or more and less than 1.0 C: Number of times per 12 hours (including holidays) is less than 0.71 Please note that the amount used per time and the method of use will vary depending on the type of lotion and the user, so the evaluation criteria here are set only as a guideline.

[0067] Tables 1 to 4 show the evaluation results using PET containers.

[0068] In the table, the entry for 199th time in the "Number of times" column indicates that the evaluation ended at the same time as the start of the next 200th time.

[0069] <When changing the amount of dimethyl silicone oil blended and the dynamic viscosity> The test film of Example 1 used a relatively high-viscosity dimethyl silicone oil (10,000 cSt), with a blending amount of 700 parts by mass per 100 parts by mass of silicone oligomer and curing catalyst combined. As shown in Table 1, the slide-off durability for emulsion 1 of Example 1 was 0.86 times (number of times per 12 hours), resulting in a B rating. Emulsions 2, 3, and 5 also received B ratings. The slide-off durability for emulsion 4 of Example 1 was 1.11 times, and the slide-off durability for ink was 1.08 times, resulting in an A rating for all. In particular, the composition of the dispersion component (23.9) and polar component (0.3) of the ink's surface free energy is similar to the composition of the dispersion component (21.4) and polar component (0.9) of dimethyl silicone oil (10,000 cSt). Normally, the two components would attract each other, but in this example, the ink slid off well against the dimethyl silicone oil on the film surface.

[0070] In contrast, the test film of Comparative Example 1 uses a relatively high-viscosity dimethyl silicone oil (10,000 cSt), but the blended amount is only 350 parts by mass, relative to a total of 100 parts by mass of silicone oligomer and curing catalyst. The slide-down durability of Comparative Example 1 for Emulsion 1 was 0.51 times (number of times per 12 hours), resulting in a C rating. The test film of Comparative Example 2 further reduced the combined blended amount of dimethyl silicone oil and curing catalyst to 100 parts by mass. Therefore, the slide-down durability of Comparative Example 2 for Emulsion 1 was 0.28 times, resulting in a C rating. From these results, it can be said that when a relatively viscous dimethyl silicone oil is contained in the sliding film, the amount of the oil to be blended should be 500 parts by mass or more per 100 parts by mass of the total of the silicone oligomer and curing catalyst.

[0071] In addition, the test film of Example 2 was prepared under the same conditions as Example 1, except that a dimethyl silicone oil with a lower viscosity (3,000 cSt) than that of Example 1 was used. The slip resistance for emulsion 1 was 0.74 times, earning a rating of B. For emulsion 2, the slip resistance was 1.44 times, earning an A rating. The slip resistance against emulsion 6 was 0.82 times, earning a rating of B.

[0072] [Table 1]

[0073] Next, for the test film of Example 3, a dimethyl silicone oil with an even lower viscosity (1,000 cSt) was used, and the other conditions were the same as those of Example 1. The slip resistance for emulsion 1 was 0.96 times, earning a rating of B. For emulsion 2 and emulsion 6, the slip resistance was 1.39 times and 1.14 times, respectively, and an A rating was obtained.

[0074] The test film of Example 4 was prepared under the same conditions as Example 1, except that a dimethyl silicone oil with a lower viscosity (500 cSt) was used. The slip resistance against emulsion 1 was 0.98 times, earning a rating of B. For emulsion 2 and emulsion 6, the slip resistance was 1.43 times and 1.10 times, respectively, and an A rating was obtained.

[0075] On the other hand, dimethyl silicone oil with a kinematic viscosity lower than 500 cSt (30 to 200 cSt) was used in the test films of Comparative Examples 4 to 7. The total blend amount of dimethyl silicone oil and curing catalyst was 700 parts by mass in all cases. The slide-down durability of Comparative Example 4 (200 cSt) against emulsion 1, emulsion 2, and emulsion 6 was 0.25 times, which was rated C. Similarly, the slide-down durability of Comparative Example 5 (100 cSt) against emulsion 1 was 0.06 times (rated C), the slide-down durability of Comparative Example 6 (50 cSt) against emulsion 1 and emulsion 2 was 0.05 times and 0.50 times (both rated C), and the slide-down durability of Comparative Example 7 (30 cSt) against emulsion 1 and emulsion 2 was 0.04 times and 0.06 times (both rated C), all of which were low ratings. From these results, it can be said that when dimethyl silicone oil is to be contained in the sliding film, it is better to use one with a relatively high viscosity (500 to 500,000 cSt).

[0076] <When reactive silicone oil is used instead of dimethyl silicone oil> Next, reactive silicone oil was used instead of dimethyl silicone oil in the test films of Comparative Examples 8 and 9. The amount of reactive silicone oil blended was 700 parts by mass in both cases. In Comparative Example 8 (side-chain carboxyl group-modified silicone oil: 2,000 cSt), the viscosity of the modified silicone oil was so high that it gelled during the paint preparation stage, making it impossible to form a test film, as shown in Table 1. The slide-off durability of Comparative Example 9 (single-terminal diol-modified silicone oil: 500 cSt) against Emulsion 6 was 0.45 times (number of times per 12 hours), earning it a rating of C. These results show that the use of non-reactive dimethyl silicone oil is superior to the use of reactive silicone oil in terms of resistance to slippage in aqueous emulsions.

[0077] The test film of Comparative Example 12 was a film containing only dimethyl silicone oil without using any silicone oligomer, and did not exhibit any sliding properties with respect to emulsion 1 (rating C). No test film was formed in Comparative Example 13. The slide-off durability of the base material itself was evaluated against emulsions 1 to 7, liquid foundation, and ink, and all were rated C.

[0078] <When using a mixture of dimethyl silicone oils with different kinematic viscosities> Next, the test film of Example 5 shown in Table 2 uses two types of dimethyl silicone oil: a relatively high viscosity dimethyl silicone oil (10,000 cSt) and a relatively low viscosity dimethyl silicone oil (100 cSt), and the blending amount of each dimethyl silicone oil is 350 parts by mass for a total of 100 parts by mass of silicone oligomer and curing catalyst. The slip-off durability for emulsion 6 and emulsion 7 of Example 5 was 0.88 times and 0.78 times (both times per 12 hours), and was evaluated as B. The slip-off durability for liquid foundation was 0.71 times, and was also evaluated as B.

[0079] [Table 2]

[0080] <When silicone resin is used instead of silicone oligomer> Next, the test films of Comparative Examples 21 to 26 shown in Table 3 used silicone resin and solvent instead of moisture-curing silicone oligomer (and moisture-curing catalyst). The amount of dimethyl silicone oil was 25 to 700 parts by mass per 100 parts by mass of silicone resin. For example, in Comparative Example 21, the amounts of dimethyl silicone oil and solvent per 100 parts by mass of silicone resin were 300 parts by mass and 200 parts by mass, respectively. The test films of Comparative Examples 21 to 24 were all rated C for durability against emulsion 1, and the test films of Comparative Examples 25 and 26 were also rated C for durability against liquid foundation. These results show that the use of a silicone oligomer, which has a small molecular weight and acts as a solvent, is superior in terms of slip resistance to aqueous emulsions compared to the use of a silicone resin and a solvent.

[0081] [Table 3]

[0082] [Table 4]

[0083] <When coated with dimethyl silicone oil diluted with a solvent> In Comparative Examples 31 to 35 shown in Table 4, test films were formed using dimethyl silicone oil diluted with a solvent. For example, in Comparative Example 31, the blending amount of solvent was 50 parts by mass per 100 parts by mass of dimethyl silicone oil (1.5-fold dilution). In Comparative Examples 32 to 35, the blending amount of solvent was determined to achieve the respective dilution ratio. Only in Comparative Example 35, a drying treatment at 100°C for 30 seconds was carried out after application. The test films of Comparative Examples 31 to 33 were all rated C for their durability against emulsion 1, and the test films of Comparative Examples 34 and 35 were also rated C for their durability against emulsion 5. These results show that when dimethyl silicone oil is used alone, even if it is diluted with a solvent to form a film, it is unable to exhibit the excellent slip resistance against aqueous emulsions that can be achieved when silicone oligomers are used.

[0084] As described above, the test results using various aqueous emulsions show that by forming the sliding film of this embodiment on the inner surface of the storage container, the sliding properties of the aqueous emulsion are maintained for a long time, and sliding durability sufficient for practical use is obtained.

[0085] <Micrograph of the surface of the decidua> Furthermore, five different coating compositions were prepared using the coating composition of Example 1, each varying in the blend ratio of the total silicone oligomer and curing catalyst to dimethyl silicone oil (10,000 cSt), and then coated onto a glass slide. After coating, the glass slide was stored in a vertical position, and the surface of the coating was observed under a microscope one day later, resulting in the 200x magnification micrographs shown in Figure 5 (only Photo 5 was at 2,000x magnification). The blend ratios and coating amounts for the coatings in Photos 1 to 6 are as follows: Mixing ratio Application amount ---------------------------------------------------------------------------------- Photo 1 Silicone oil only 30g / m 2 Photo 2 1:7 33g / m 2 Photo 3 1:3.5 12g / m 2 Photos 4, 5 1:1 27g / m 2 Photo 6 Silicone oligomer and curing catalyst only 4g / m 2 ----------------------------------------------------------------------------------

[0086] In the film with the same blend ratio of 1:7 as in Example 1 (Photo 2), when the dimethyl silicone oil is considered to be an ocean, the cured moisture-curable silicone oligomer can be observed to be distributed in the form of numerous islands on the order of micrometers. In this way, a "mosaic surface structure" consisting of the cured relatively low molecular weight silicone oligomer and the relatively high molecular weight silicone oil is formed. The distribution of the cured silicone oligomer as shown in Photo 2 could not be confirmed in films containing only dimethyl silicone oil, other blend ratios (1:3.5 and 1:1), or silicone oligomer only (Photos 1, 3-6). Furthermore, when a mixture of two or more dimethyl silicone oils with different viscosities is used, a "mosaic surface structure" consisting of the relatively low molecular weight silicone oil and the relatively high molecular weight silicone oil is also formed. When an aqueous emulsion comes into contact with such a sliding film, the dimethyl silicone oil present on the surface slides the aqueous emulsion, providing excellent sliding properties for the aqueous emulsion. [Explanation of symbols]

[0087] 1 Base material 10 synovium 12 Moisture-curing silicone oligomer 14 Moisture-curing catalyst 16 Dimethyl silicone oil 20 Aqueous emulsion

Claims

1. A sliding film formed on the surface of a substrate, (A) a cured product of a moisture-curable silicone oligomer; (B) a curing catalyst for moisture curing; and (C) A kinematic viscosity at 25°C of 500 to 500,000 mm ２ / s, dimethyl silicone oil, A sliding film characterized in that the blending amount of component (C) is 500 to 800 parts by mass per 100 parts by mass of the total of components (A) and (B), and that causes an aqueous emulsion to slide off.

2. A sliding film formed on the surface of a substrate, (A) a cured product of a moisture-curable silicone oligomer; (B) a curing catalyst for moisture curing; and (C) dimethyl silicone oil, Component (C) has a kinematic viscosity at 25°C of 500,000 to 500,000 mm ２ A mixture of two or more dimethyl silicone oils having kinematic viscosities selected from the group consisting of dimethyl silicone oils having kinematic viscosities of 700,000 to 400,000 mm / s, ２ / s, A sliding film characterized in that the blending amount of component (C) is 500 to 800 parts by mass per 100 parts by mass of the total of components (A) and (B), and that causes an aqueous emulsion to slide off.

3. A sliding film formed on the surface of a substrate, (A) a cured product of a moisture-curable silicone oligomer; (B) a curing catalyst for moisture curing; (C) A kinematic viscosity at 25°C of 500 to 500,000 mm ２ / s dimethyl silicone oil, and (D) A kinematic viscosity at 25°C of 50 mm ２ / s or more, 500mm ２ One or more dimethyl silicone oils having a kinematic viscosity of less than 1 / s are contained, the combined amount of the (C) component and the (D) component is 500 to 800 parts by mass per 100 parts by mass of the combined amount of the (A) component and the (B) component; The kinematic viscosity of the dimethyl silicone oil, which is a mixture of components (C) and (D), is 150,000 to 200,000 mm ２ / s range, and causes the aqueous emulsion to slide off.

4. The mass per area of ​​the sliding film is 10 to 65 g / m ２ 4. The sclerotial membrane according to claim 1, wherein:

5. A container for aqueous emulsions, characterized in that the sliding film according to any one of claims 1 to 3 is formed on the inner surface thereof.

6. A container containing an aqueous emulsion, The surface free energy of the aqueous emulsion contained in the container is 24 to 33 mJ / m ２ and A container containing an aqueous emulsion, wherein the inner surface of the container is formed with the sliding film according to any one of claims 1 to 3.

Images