Shedding film, laminate, and packaging container

Abstract

Provided is a shedding film that is formed from an alkyl trialkoxysilane (A) with a C1-14 alkyl group, a tetraalkoxysilane (B), and a dialkyl dialkoxysilane (C).

Description

Sliding membrane, laminate and packaging container

[0001] The present invention relates to a sliding film, a laminate, and a packaging container, and more particularly to a sliding film that is excellent in transparency and flexibility and has excellent sliding properties against adhesions, as well as a laminate and a packaging container that include such a sliding film.

[0002] Edible oils are generally distributed and used in packaging containers made of resins such as polyethylene and polyethylene terephthalate, or glass or metal. Due to the low surface tension of edible oils, when used in a packaging container, they tend to wet and spread over the inner surface of the packaging container. Therefore, when the amount of edible oil remaining in the packaging container is low, it becomes difficult to discharge the oil from the packaging container, which poses a problem of making it difficult to reduce the unavoidable remaining amount.

[0003] In response to this, for example, studies have been conducted to improve oil repellency using a fluorine-based material, thereby suppressing adhesion to a packaging container made of resin (see, for example, Patent Document 1). However, the method of improving oil repellency using a fluorine-based material has problems such as the fluorine-based material itself being expensive, the treatment equipment being large-scale, the treatment time required to improve oil repellency being long, and the transparency of the packaging container made of resin being impaired.

[0004] Japanese Patent Application Laid-Open No. 2021-37650

[0005] An object of the present invention is to provide a sliding film that is excellent in transparency and flexibility and has excellent sliding properties against deposits.

[0006] The present inventors have conducted extensive research to solve the above problems and have found that a sliding film formed from an alkyltrialkoxysilane (A) having an alkyl group with 1 to 14 carbon atoms, a tetraalkoxysilane (B), and a dialkyldialkoxysilane (C) can achieve excellent transparency, flexibility, and sliding properties, thereby completing the present invention. That is, the present invention provides the following inventions [1] to

[13] .

[0007] [1] A sliding film formed from an alkyltrialkoxysilane (A) having an alkyl group of 1 to 14 carbon atoms, a tetraalkoxysilane (B), and a dialkyldialkoxysilane (C). [2] The sliding film according to [1], which contains a cohydrolyzate or condensation polymer of the alkyltrialkoxysilane (A), the tetraalkoxysilane (B), and the dialkyldialkoxysilane (C). [3] The sliding film according to [1] or [2], wherein the alkyltrialkoxysilane (A) contains an alkyl group having 2 to 12 carbon atoms, and at least one of the two alkyl groups contained in the dialkyldialkoxysilane (C) has a carbon number smaller than that of the alkyl group contained in the alkyltrialkoxysilane (A). [4] The sliding film according to [3], wherein both of the two alkyl groups contained in the dialkyldialkoxysilane (C) have a carbon number smaller than that of the alkyl group contained in the alkyltrialkoxysilane (A). [5] The sliding film according to any one of [1] to [4], wherein both of the two alkyl groups contained in the dialkyldialkoxysilane (C) are methyl groups. [6] The sliding film according to any one of [1] to [5], wherein the molar ratio of the dialkyldialkoxysilane (C) to the total of the alkyltrialkoxysilane (A), the tetraalkoxysilane (B), and the dialkyldialkoxysilane (C) (dialkyldialkoxysilane (C) / (alkyltrialkoxysilane (A) + tetraalkoxysilane (B) + dialkyldialkoxysilane (C))) is 0.01 to 0.20. [7] The sliding film according to any one of [1] to [6], wherein the pencil hardness is 2H or less. [8] A laminate obtained by laminating the sliding film according to any one of [1] to [7] and a resin substrate. [9] A packaging container comprising a container body obtained by laminating the sliding film according to any one of [1] to [7] and a resin substrate.

[10] The packaging container according to [9], wherein the resin substrate is a substrate made of polyethylene terephthalate.

[11] The packaging container according to claim [9] or

[10] , which is for edible oil.

[12] The packaging container according to

[11] , wherein the edible oil is at least one selected from the group consisting of rapeseed oil, canola oil, refined rapeseed oil, soybean oil, corn oil, cottonseed oil, peanut oil, sesame oil, rice oil, rice bran oil, camellia oil, safflower oil, olive oil, linseed oil, perilla oil, perilla oil, sunflower oil, coconut oil, tea oil, avocado oil, kukui nut oil, grapeseed oil, cocoa butter, wheat germ oil, almond oil, evening primrose oil, castor oil, hazelnut oil, macadamia nut oil, rosehip oil, and grape oil, and oils made from these raw materials.

[13] A method for producing a gliding film, comprising a step of co-hydrolyzing or condensing an alkyltrialkoxysilane (A) having an alkyl group of 1 to 14 carbon atoms, a tetraalkoxysilane (B), and a dialkyldialkoxysilane (C).

[0008] According to the present invention, it is possible to provide a sliding film that is excellent in transparency and flexibility and has excellent sliding properties against deposits.

[0009] <Sliding film> The sliding film of the present invention is formed from an alkyltrialkoxysilane (A) having an alkyl group with 1 to 14 carbon atoms, a tetraalkoxysilane (B), and a dialkyldialkoxysilane (C). The sliding film of the present invention is a film-like molded article that has the ability to slide off deposits, and in particular is a film-like molded article that has excellent transparency and flexibility and has excellent sliding off properties against deposits.

[0010] The sliding film of the present invention is not particularly limited as long as it is formed from an alkyltrialkoxysilane (A) having an alkyl group with 1 to 14 carbon atoms (hereinafter simply referred to as "alkyltrialkoxysilane (A)"), a tetraalkoxysilane (B), and a dialkyldialkoxysilane (C), but preferably contains a co-hydrolyzate or condensation polymer of the alkyltrialkoxysilane (A), the tetraalkoxysilane (B), and the dialkyldialkoxysilane (C).

[0011] The alkyltrialkoxysilane (A) is a silane compound having one alkyl group and three alkoxy groups, where the alkyl group has 1 to 14 carbon atoms. Examples of the alkyltrialkoxysilane (A) include compounds represented by the following general formula (1):

[0012] In the above general formula (1), R １ is an alkyl group having 1 to 14 carbon atoms, preferably an alkyl group having 2 to 12 carbon atoms, and more preferably an alkyl group having 6 to 10 carbon atoms, in order to further increase the flexibility of the sliding film. １ Although R may be a linear alkyl group or a branched alkyl group, it is preferable that R be a linear alkyl group from the viewpoint of further improving the sliding property. １ may be an alkyl group having a substituent or an alkyl group having no substituent, but is preferably an alkyl group having no substituent. １ is C ｎ H ２ｎ＋１ (n=1 to 14) is preferred.

[0013] R １ Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, and an n-tetradecyl group. Among these, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-pentyl group, an n-undecyl group, and an n-dodecyl group are preferred, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group are more preferred, and an n-octyl group is particularly preferred.

[0014] In the above general formula (1), R ２ ~R ４are each independently an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. ２ ~R ４ may be a linear alkyl group or a branched alkyl group, but is preferably a linear alkyl group. ２ ~R ４ may be an alkyl group having a substituent or an alkyl group having no substituent, but is preferably an alkyl group having no substituent. ２ ~R ４ is C ｍ H ２ｍ＋１ (m=1 to 4). ２ ~R ４ may be different groups or may be the same group, but R ２ ~R ４ are preferably all the same group.

[0015] R ２ ~R ４ Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group. Among these, a methyl group, an ethyl group, an n-propyl group, and an n-butyl group are preferred, a methyl group and an ethyl group are more preferred, and an ethyl group is particularly preferred.

[0016] Specific examples of the alkyltrialkoxysilane (A) include methyltriethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, n-butyltriethoxysilane, n-pentyltriethoxysilane, n-hexyltriethoxysilane, n-heptyltriethoxysilane, n-octyltriethoxysilane, n-nonyltriethoxysilane, n-decyltriethoxysilane, n-undecyltriethoxysilane, n-dodecyltriethoxysilane, n-tridecyltriethoxysilane, and n-tetradecyltriethoxysilane. Among these, n-octyltriethoxysilane is preferred. The alkyltrialkoxysilane (A) may be used alone or in combination of two or more.

[0017] The tetraalkoxysilane (B) is a silane compound having four alkoxy groups, and examples of the tetraalkoxysilane (B) include compounds represented by the following general formula (2).

[0018] In the above general formula (2), R ５ ~R ８ are each independently an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. ５ ~R ８ may be a linear alkyl group or a branched alkyl group, but is preferably a linear alkyl group. ５ ~R ８ may be an alkyl group having a substituent or an alkyl group having no substituent, but is preferably an alkyl group having no substituent. ５ ~R ８ is C ｍ H ２ｍ＋１ (m=1 to 4) is preferred. ５ ~R ８ Specific examples of R ２ ~R ４ Specific examples of R include the same as those of R, and a methyl group and an ethyl group are more preferred, with an ethyl group being particularly preferred. ５ ~R ８ may be different groups or may be the same group, but R ５ ~R ８ are preferably all the same group, and in particular, R ５ ~R ８ are all the same group, and R in the general formula (1) ２ ~R ４ And, R ５ ~R ８ It is preferred that all of the groups are the same.

[0019] Specific examples of the tetraalkoxysilane (B) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, ethoxytrimethoxysilane, diethoxydimethoxysilane, and triethoxymethoxysilane. Among these, tetraethoxysilane is preferred. The tetraalkoxysilane (B) may be used alone or in combination of two or more.

[0020] The dialkyldialkoxysilane (C) is a silane compound having two alkyl groups and two alkoxy groups. Examples of the dialkyldialkoxysilane (C) include a compound represented by the following general formula (3):

[0021] In the above general formula (3), R ９ , R １０ are each independently an alkyl group, and from the viewpoint of being able to further increase the flexibility of the sliding film, are preferably alkyl groups having 1 to 8 carbon atoms, more preferably alkyl groups having 1 to 4 carbon atoms, and even more preferably alkyl groups having 1 to 3 carbon atoms. ９ , R １０ Although R may be a linear alkyl group or a branched alkyl group, it is preferable that R be a linear alkyl group in order to further increase the flexibility of the sliding film. ９ , R １０ may be an alkyl group having a substituent or an alkyl group having no substituent, but is preferably an alkyl group having no substituent. ９ , R １０ is C ｎ H ２ｎ＋１ (n=1 to 3) is preferred.

[0022] Also, R ９ , R １０ The alkyl group contained in the alkyltrialkoxysilane (A) (for example, R １ and R ９ , R１０ At least one of the alkyl groups contained in the alkyltrialkoxysilane (A) (for example, R １ It is preferable that the alkyl group has fewer carbon atoms than the alkyl group represented by R １ is an n-propyl group, R ９ , R １０ at least one of R is preferably a methyl group or an ethyl group; ９ , R １０ It is more preferable that both of R are alkyl groups having fewer carbon atoms than the alkyl group contained in the alkyltrialkoxysilane (A), even more preferable that they are alkyl groups having 3 to 7 fewer carbon atoms than the alkyl group contained in the alkyltrialkoxysilane (A), and particularly preferable that they are alkyl groups having 5 to 7 fewer carbon atoms. ９ , R １０ may be different groups or may be the same group, but R ９ , R １０ are preferably the same group.

[0023] R ９ , R １０ Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group. Among these, a methyl group, an ethyl group, an n-propyl group, and an n-butyl group are preferred, a methyl group and an ethyl group are more preferred, and a methyl group is particularly preferred.

[0024] In the above general formula (3), R １１ , R １２ are each independently an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. １１ , R １２ may be a linear alkyl group or a branched alkyl group, but is preferably a linear alkyl group. １１ , R １２may be an alkyl group having a substituent or an alkyl group having no substituent, but is preferably an alkyl group having no substituent. １１ , R １２ is C ｍ H ２ｍ＋１ (m=1 to 4) is preferred. １１ , R １２ Specific examples of R ２ ~R ４ Specific examples of R include the same as those of R, and a methyl group and an ethyl group are more preferred, with an ethyl group being particularly preferred. １１ , R １２ may be different groups or may be the same group, but R １１ , R １２ are preferably all the same group, and in particular, R １１ , R １２ are all the same group, and R in the general formula (1) ２ ~R ４ And, R １１ , R １２ It is preferred that all of the groups are the same.

[0025] Specific examples of dialkyldialkoxysilane (C) include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dimethyldiisopropoxysilane, diethyldiisopropoxysilane, diethyldibutoxysilane, octylmethyldimethoxysilane, octylmethyldiethoxysilane, octylmethyldiisopropoxysilane, octylmethyldiisopropoxysilane, etc. Among these, dimethyldiethoxysilane is preferred. Dialkyldialkoxysilane (C) may be used alone or in combination of two or more.

[0026] The ratio of alkyltrialkoxysilane (A), tetraalkoxysilane (B), and dialkyldialkoxysilane (C) in the sliding film of the present invention is not particularly limited, but from the viewpoint of being able to further improve the sliding properties of the sliding film, the molar ratio of dialkyldialkoxysilane (C) to the total of alkyltrialkoxysilane (A), tetraalkoxysilane (B), and dialkyldialkoxysilane (C) (dialkyldialkoxysilane (C) / (alkyltrialkoxysilane (A) + tetraalkoxysilane (B) + dialkyldialkoxysilane (C))) is preferably in the range of 0.01 to 0.20, more preferably in the range of 0.02 to 0.16, and even more preferably in the range of 0.04 to 0.12.

[0027] In addition, in the sliding film of the present invention, the molar ratio of alkyltrialkoxysilane (A) to the total of alkyltrialkoxysilane (A), tetraalkoxysilane (B), and dialkyldialkoxysilane (C) (alkyltrialkoxysilane (A) / (alkyltrialkoxysilane (A) + tetraalkoxysilane (B) + dialkyldialkoxysilane (C))) is preferably in the range of 0.01 to 0.50, more preferably in the range of 0.05 to 0.40, and even more preferably in the range of 0.10 to 0.30, in order to further increase the flexibility of the sliding film.

[0028] Furthermore, in the sliding film of the present invention, the molar ratio of tetraalkoxysilane (B) to the total of alkyltrialkoxysilane (A), tetraalkoxysilane (B), and dialkyldialkoxysilane (C) (tetraalkoxysilane (B) / (alkyltrialkoxysilane (A) + tetraalkoxysilane (B) + dialkyldialkoxysilane (C))) is preferably in the range of 0.30 to 0.98, more preferably in the range of 0.44 to 0.93, and even more preferably in the range of 0.58 to 0.86, in order to further increase the flexibility of the sliding film.

[0029] The method for producing the sliding film of the present invention is not particularly limited, but for example, a method of co-hydrolysis or condensation polymerization of an alkyltrialkoxysilane (A), a tetraalkoxysilane (B), and a dialkyldialkoxysilane (C) can be mentioned.

[0030] Methods for co-hydrolyzing or condensation-polymerizing alkyltrialkoxysilane (A), tetraalkoxysilane (B), and dialkyldialkoxysilane (C) include, but are not limited to, co-hydrolyzing or condensation-polymerizing alkyltrialkoxysilane (A), tetraalkoxysilane (B), and dialkyldialkoxysilane (C) in the presence of a catalyst. Acid catalysts are preferred. Acid catalysts include, but are not limited to, sulfuric acid, nitric acid, organic sulfonic acids such as dodecylbenzenesulfonic acid, oxalic acid, hydrochloric acid, and acetic acid. Among these, hydrochloric acid, organic sulfonic acids such as dodecylbenzenesulfonic acid, and oxalic acid are preferred, with hydrochloric acid being more preferred. It is preferable to adjust the pH of the film-sliding solution to less than 4. Alternatively, hydrolysis may be completed under acidic conditions, followed by the addition of a base to adjust the pH to a range of 4 to 9 to promote the polymerization reaction. The base catalyst is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, ammonia, urea, and amine compounds such as octylamine. Among these, ammonia, urea, and amine compounds such as octylamine are preferred, and ammonia is more preferred. The acid catalyst and the base catalyst may be used alone or in combination of two or more.

[0031] The amount of water required for hydrolysis is preferably greater than the number of alkoxy groups in the solution, in order to hydrolyze all alkoxy groups contained in the solution and generate silanol groups. The amount of water used for hydrolysis is not particularly limited, but it is also preferable to use a relatively small amount in order to further improve the sliding properties of the film.

[0032] Furthermore, when the alkyltrialkoxysilane (A), the tetraalkoxysilane (B), and the dialkyldialkoxysilane (C) are cohydrolyzed or condensed, an organic solvent may be used. The organic solvent is not particularly limited as long as it is inert to the reaction, but is preferably a solvent that is inert to the reaction and can dissolve the alkyltrialkoxysilane (A), the tetraalkoxysilane (B), and the dialkyldialkoxysilane (C). Examples of the organic solvent include aromatic hydrocarbons such as benzene and toluene; linear saturated hydrocarbons such as n-pentane and n-hexane; alicyclic saturated hydrocarbons such as cyclopentane and cyclohexane; ethers such as tetrahydrofuran, anisole, and diethyl ether; esters such as ethyl acetate and ethyl benzoate; ketones such as acetone, methyl ethyl ketone, and acetophenone; aprotic polar solvents such as acetonitrile, dimethylformamide, dimethylacetamide, and dimethyl sulfoxide; and protic polar solvents such as methanol, ethanol, isopropanol, and n-butanol. Among these, ketones and aprotic polar solvents are preferred. From the viewpoints of not inhibiting the reaction, solubility of the raw materials, miscibility with water used in hydrolysis, and ease of removal in subsequent steps, acetone, methyl ethyl ketone, acetonitrile, methanol, ethanol, and isopropanol are preferred, with methyl ethyl ketone, ethanol, and isopropanol being more preferred. The organic solvents may be used alone or in combination of two or more. The amount of organic solvent used is preferably 100 to 10,000 mol, more preferably 300 to 3,000 mol, and even more preferably 800 to 1,200 mol, per 100 mol of the total of the alkyltrialkoxysilane (A), tetraalkoxysilane (B), and dialkyldialkoxysilane (C).

[0033] In the present invention, a combination of alkyltrialkoxysilane (A), tetraalkoxysilane (B), and dialkyldialkoxysilane (C) is used. The alkyl group having 1 to 14 carbon atoms contained in the alkyltrialkoxysilane (A) suppresses shrinkage during drying when cohydrolyzed or condensed, thereby enabling the formation of a good sliding film. Additionally, in the present invention, the dialkyldialkoxysilane (C) relatively increases the alkyl group content and relatively decreases the hydroxyl group content in the sliding film, thereby reducing surface free energy and enhancing oil repellency. Furthermore, since the dialkyldialkoxysilane (C) is a bifunctional compound, it does not form crosslinks, thereby enhancing the mobility of the molecular structure in the sliding film. Furthermore, in the present invention, these effects achieved by using the dialkyldialkoxysilane (C) improve the sliding properties of the sliding film and also enable improved flexibility.

[0034] In addition, the sliding film of the present invention may contain various additives such as antioxidants, rust inhibitors, ultraviolet absorbers, light stabilizers, antifungal agents, antibacterial agents, anti-biofouling agents, deodorizers, pigments, flame retardants, and antistatic agents, as long as the effects of the present invention are not impaired.

[0035] The thickness of the sliding film of the present invention is not particularly limited, but from the viewpoint of flexibility, it is preferably 5 to 1000 nm, more preferably 10 to 400 nm, and even more preferably 20 to 200 nm.

[0036] Furthermore, from the viewpoint of being able to further increase flexibility, the sliding film of the present invention preferably has a pencil hardness of 2H or less, and more preferably a pencil hardness of B or less. In particular, when the sliding film of the present invention is used for packaging container applications, particularly for packaging container applications for edible oil, it is desired that the film has excellent flexibility in addition to excellent transparency and excellent sliding properties against adhesions, and excellent flexibility makes it possible to effectively prevent defects such as cracks from occurring in the sliding film even when the packaging container is deformed.

[0037] <Laminate, Packaging Container> The laminate of the present invention is formed by laminating the above-described sliding membrane of the present invention and a resin substrate.

[0038] The material constituting the resin substrate is not particularly limited, but thermoplastic resins can be suitably used from the viewpoint of being easily molded into various shapes.

[0039] Examples of thermoplastic resins for constituting the resin substrate include olefin-based resins such as low-density polyethylene, high-density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, or random or block copolymers of α-olefins such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, and cyclic olefin copolymers; ethylene-vinyl copolymers such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, and ethylene-vinyl chloride copolymer; styrene-based resins such as polystyrene, acrylonitrile-styrene copolymer, ABS, and α-methylstyrene-styrene copolymer; vinyl resins such as polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinylidene chloride copolymer, polymethyl acrylate, and polymethyl methacrylate; polyamide resins such as nylon 6, nylon 6-6, nylon 6-10, nylon 11, and nylon 12; polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate, and copolymer polyesters thereof; polycarbonate resins; polyphenylene oxide resins; and biodegradable resins such as polylactic acid. Among these, polyester resins are preferred, and polyethylene terephthalate (PET) is more preferred, from the viewpoints of compatibility with the sliding film of the present invention and moldability.

[0040] The method for producing the laminate of the present invention is not particularly limited, but it can be produced by preparing a film-sliding solution by dissolving or dispersing an alkyltrialkoxysilane (A), a tetraalkoxysilane (B), a dialkyldialkoxysilane (C), and a catalyst in an organic solvent, applying the prepared film-sliding solution to a resin substrate, allowing a co-hydrolysis or condensation polymerization reaction to proceed, and removing the organic solvent.

[0041] The method for applying the solution for coating a resin substrate with the coating solution is not particularly limited, and any method capable of forming a coating with the desired thickness can be used, including, for example, roll coating, casting, dipping, spin coating, die coating, bar coating, spray coating, etc. The method for removing the organic solvent is not particularly limited, and includes, for example, drying at a desired temperature.

[0042] The thickness of the sliding film in the laminate of the present invention is not particularly limited, but from the viewpoint of flexibility, it is preferably 5 to 1000 nm, more preferably 10 to 400 nm, and even more preferably 20 to 200 nm. The thickness of the resin substrate may be appropriately selected depending on the application, but is preferably 5 to 5000 μm, more preferably 100 to 2000 μm.

[0043] In addition, in the laminate of the present invention, the sliding film is formed from alkyltrialkoxysilane (A), tetraalkoxysilane (B), and dialkyldialkoxysilane (C), so sufficient reliability can be ensured even when the sliding film is formed directly on the resin substrate. Therefore, in the laminate of the present invention, it is preferable that the sliding film is formed directly on the resin substrate, and this makes it possible to manufacture a laminate with excellent reliability with high productivity.

[0044] The laminate of the present invention can be made into, for example, a packaging container having a predetermined shape. That is, it can be made into a packaging container having a container body formed by laminating the above-mentioned sliding membrane of the present invention and a resin substrate.

[0045] The method for molding the laminate of the present invention into a predetermined shape to form a packaging container is not particularly limited, but for example, a preform in the form of a sheet, pipe, test tube, or the like can be molded, and then secondary molding such as plug-assist molding or blow molding can be performed to form a packaging container in the form of a cup, tray, or bottle. The structure of the container is not particularly limited, but for example, it can be a single-layer container, a multi-layer container, a double-structure container, a delaminating container, or the like.

[0046] The packaging container of the present invention has the sliding membrane of the present invention described above, which has excellent transparency and excellent sliding properties against adhesions, so the packaging container of the present invention can take advantage of these properties and be suitably used as a packaging container for packaging edible oil.

[0047] The edible oil is not particularly limited, but examples thereof include rapeseed oil, canola oil, refined rapeseed oil, soybean oil, corn oil, cottonseed oil, peanut oil, sesame oil, rice oil, rice bran oil, camellia oil, safflower oil, olive oil, linseed oil, perilla oil, perilla oil, sunflower oil, coconut oil, tea oil, avocado oil, kukui nut oil, grapeseed oil, cocoa butter, wheat germ oil, almond oil, evening primrose oil, castor oil, hazelnut oil, macadamia nut oil, rosehip oil, and grape oil, as well as oils made from these as raw materials. These edible oils may also contain various additives, such as chili oil (a chili pepper-flavored oil made by adding chili peppers to sesame oil and heating it to give the oil a spicy flavor), emulsified liquid dressings (such as an emulsified liquid dressing containing sesame), or separated liquid dressings (such as a separated liquid dressing containing green shiso).The edible oil may also be oils made from the above-mentioned oils, such as MCT oil (oil obtained by extracting neutralized fatty acids from palm oil, coconut oil, etc.).

[0048] The packaging container of the present invention has the sliding membrane of the present invention described above, which gives it excellent sliding properties against adhesions.For example, when used as a packaging container for packaging edible oil, the edible oil contained therein can be sufficiently slid off, thereby appropriately reducing the amount of edible oil that inevitably remains as a content.

[0049] Therefore, by reducing the amount of unavoidable residual edible oil, it is possible to contribute to reducing food waste and also to excellent recyclability as a packaging container. More specifically, it is possible to reduce the amount of washing water used during cleaning during recycling. Furthermore, when the packaging container is made into a recycled material, components derived from the sliding film will be contained along with the resin base material that constitutes the packaging container. However, the components derived from the sliding film, specifically, the alkyltrialkoxysilane (A), tetraalkoxysilane (B), and dialkyldialkoxysilane (C), do not have a negative effect on the recycled material and can be easily removed by alkaline cleaning, etc. Therefore, from this perspective, it is possible to achieve excellent recyclability and appropriately contribute to the realization of a circular society.

[0050] Next, the present invention will be specifically explained by way of examples, but the present invention is not limited to these examples.

[0051] Example 1 (Preparation of a solution for film sliding) n-octyltriethoxysilane as the alkyltrialkoxysilane (A), tetraethoxysilane as the tetraalkoxysilane (B), and dimethyldiethoxysilane as the dialkyldialkoxysilane (C) were used in the proportions shown in Table 1, to which ethanol and a 0.01 M aqueous hydrochloric acid solution were added, and the mixture was stirred at 23°C for 24 hours to allow a condensation polymerization reaction to proceed. Next, ethanol was added to the solution after stirring for 24 hours, diluting it 10 times by weight, and the mixture was stirred at 23°C for 10 minutes to obtain a solution for film sliding.

[0052] (Preparation of a laminate sample using a glass substrate) The solution for the film-sliding obtained above was spin-coated onto a glass slide (product name "Slide Glass S7213", manufactured by Matsunami Glass Co., Ltd.) as a glass substrate, and then dried for 24 hours under conditions of 23 ° C. and 50% RH to obtain a laminate sample using a glass substrate. The spin-coating conditions were 3000 rpm and 20 seconds, and the film-sliding was formed to a thickness of approximately 30 nm.

[0053] (Preparation of a laminate sample using PET as a substrate) The solution for film sliding obtained above was spin-coated onto a 10 cm x 10 cm, 250 μm thick polyethylene terephthalate film (product name "Lumirror T60 #250", manufactured by Toray Industries, Inc.) as a resin substrate, and then dried for 24 hours at 23 ° C. and 50% RH to obtain a laminate sample using PET as a substrate. The spin-coating conditions were 3000 rpm and 20 seconds, and a film sliding thickness of approximately 30 nm was formed.

[0054] (Pencil Hardness Measurement) The pencil hardness of the glass-based laminate samples obtained above was measured in accordance with the pencil hardness test specified in JIS K5600-5-4:1999 "General test methods for coatings - Part 5: Mechanical properties of coating films - Section 4: Scratch hardness (pencil method)". The results are shown in Table 1.

[0055] (Contact Angle Measurement) The contact angle of the PET-based laminate sample obtained above with canola oil (edible rapeseed oil, product name "Nissin Canola Oil", manufactured by Nisshin Oillio Co., Ltd.) was measured by the sessile drop method (analysis method: tangent method, liquid volume: 2.0 μL) using a contact angle meter (DropMaster 700, manufactured by Kyowa Interface Science Co., Ltd.). The average value of 10 measurements was taken as the contact angle value, and the obtained results are shown in Table 2.

[0056] (Measurement of sliding angle) The sliding angle of the laminate sample using the PET substrate obtained above to canola oil (edible rapeseed oil, product name "Nissin Canola Oil", manufactured by Nisshin Oillio Co., Ltd.) was measured using a contact angle meter (DropMaster 700, manufactured by Kyowa Interface Science Co., Ltd.) by the sliding method (analysis method: tangent method, liquid volume: 10.0 μL, tilt method: continuous tilt, sliding detection: after sliding, movement judgment: receding contact angle, sliding judgment distance: 0.093 mm). The average value of 10 measurements was taken as the sliding angle value, and the obtained results are shown in Table 2.

[0057] Examples 2 to 9, Comparative Example 1 A film-sliding solution was prepared in the same manner as in Example 1, except that the amounts of n-octyltriethoxysilane as the alkyltrialkoxysilane (A), tetraethoxysilane as the tetraalkoxysilane (B), and dimethyldiethoxysilane as the dialkyldialkoxysilane (C), as well as the amounts of ethanol and 0.01 M hydrochloric acid aqueous solution used, were as shown in Table 1. A laminate sample having a glass substrate and a laminate sample having a PET substrate were prepared using this solution.

[0058] The pencil hardness of the obtained laminate sample having a glass substrate was measured in the same manner as in Example 1. The results are shown in Table 1. The contact angle and sliding angle of the obtained laminate sample having a PET substrate were measured in the same manner as in Example 1. The results are shown in Table 2.

[0059]

[0060]

[0061] As shown in Tables 1 and 2, the sliding films formed from alkyltrialkoxysilane (A) having an alkyl group with 1 to 14 carbon atoms, tetraalkoxysilane (B), and dialkyldialkoxysilane (C) had low pencil hardness, excellent flexibility, and a high contact angle with canola oil, a small sliding angle, and excellent sliding properties against deposits. Furthermore, the sliding films formed from alkyltrialkoxysilane (A) having an alkyl group with 1 to 14 carbon atoms, tetraalkoxysilane (B), and dialkyldialkoxysilane (C) were formed using alkylalkoxysilane compounds and alkoxysilane compounds, and therefore had the transparency inherent in these compounds, and therefore also had excellent transparency.

[0062] Example 10 (Preparation of a Packaging Container Sample) A polyethylene terephthalate bottle (a 600 g square PET bottle) was placed upright, and the inner surface of the PET bottle was spray-coated with the solution for film-sliding (approximately 1 mL) prepared in Example 4. After that, the bottle was dried for 5 minutes while blowing hot air, and a film-sliding of 20 to 300 nm was formed inside the PET bottle.

[0063] (Evaluation of residual amount in packaging container sample) The PET bottle obtained above was filled with 600 g of canola oil in advance, and then tilted upside down at a speed of 10° / sec to pour out the canola oil filled inside. The amount of canola oil remaining 2 minutes after being in the inverted state was measured. Furthermore, the PET bottle used for the above evaluation was refilled with 15 g of canola oil, and then tilted upside down at a speed of 10° / sec to pour out the canola oil filled inside again. The amount of canola oil remaining 30 seconds after being in the inverted state was measured. The same evaluation as above was also performed on an untreated PET bottle (a PET bottle without a sliding film), and the reduction rate (%) relative to the amount remaining in the untreated PET bottle was calculated using the following formula to evaluate the residual amount. Reduction rate (%) = ("Remaining amount (g) of untreated PET bottle" - "Remaining amount (g) of PET bottle of Example 10") / "Remaining amount (g) of untreated PET bottle" x 100) In this case, the reduction rate when filled with 600 g of canola oil was 81%, and when refilled with 15 g of canola oil, the reduction rate was 75%, suggesting that the PET bottle having the sliding film of the present invention has excellent sliding properties and can reduce the remaining amount.

Claims

1. A sliding film formed from an alkyltrialkoxysilane (A) having an alkyl group with 1 to 14 carbon atoms, a tetraalkoxysilane (B), and a dialkyldialkoxysilane (C).

2. The sliding film according to claim 1, comprising a cohydrolyzate or condensation polymer of the alkyltrialkoxysilane (A), the tetraalkoxysilane (B), and the dialkyldialkoxysilane (C).

3. The sliding film according to claim 1 or 2, wherein the alkyl trialkoxysilane (A) contains an alkyl group having 2 to 12 carbon atoms as the alkyl group, and at least one of the two alkyl groups contained in the dialkyl dialkoxysilane (C) is an alkyl group having a smaller number of carbon atoms than the alkyl group contained in the alkyl trialkoxysilane (A).

4. The sliding film described in claim 3, wherein the two alkyl groups contained in the dialkyldialkoxysilane (C) each have a smaller number of carbon atoms than the alkyl group contained in the alkyltrialkoxysilane (A).

5. The sliding film according to claim 1 or 2, wherein the two alkyl groups contained in the dialkyldialkoxysilane (C) are both methyl groups.

6. The sliding film according to claim 1 or 2, wherein the molar ratio of the dialkyl dialkoxy silane (C) to the total of the alkyl trialkoxy silane (A), the tetraalkoxy silane (B), and the dialkyl dialkoxy silane (C) (dialkyl dialkoxy silane (C) / (alkyl trialkoxy silane (A)+tetraalkoxy silane (B)+dialkyl dialkoxy silane (C))) is 0.01 to 0.

20.

7. The sclerotial film according to claim 1 or 2, having a pencil hardness of 2H or less.

8. A laminate comprising the sliding film according to claim 1 or 2 and a resin substrate.

9. A packaging container comprising a container body formed by laminating the sliding membrane according to claim 1 or 2 and a resin substrate.

10. The packaging container according to claim 9, wherein the resin substrate is a polyethylene terephthalate substrate.

11. A packaging container according to claim 9 or 10, which is for edible oil.

12. The packaging container according to claim 11, wherein the edible oil comprises at least one selected from the group consisting of rapeseed oil, canola oil, rapeseed oil, soybean oil, corn oil, cottonseed oil, peanut oil, sesame oil, rice oil, rice bran oil, camellia oil, safflower oil, olive oil, linseed oil, perilla oil, perilla oil, sunflower oil, coconut oil, coconut oil, tea oil, avocado oil, kukui nut oil, grapeseed oil, cocoa butter, wheat germ oil, almond oil, evening primrose oil, castor oil, hazelnut oil, macadamia nut oil, rosehip oil, and grape oil, as well as oils made from these raw materials.

13. A method for producing a sliding film, comprising a step of co-hydrolyzing or condensing an alkyltrialkoxysilane (A) having an alkyl group having 1 to 14 carbon atoms, a tetraalkoxysilane (B), and a dialkyldialkoxysilane (C).

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