Film

Abstract

To provide a film that exhibits a smooth surface, excellent aesthetic quality, and a high capability of preserving food freshness.SOLUTION: A film having an oxygen permeability of 120 to 7000 cm3 / m2 day atm at 23°C.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a film. [Background technology]

[0002] Traditionally, wrap films have been used in many ordinary households as wrap films for food, etc., due to their excellent properties, such as adhesion to other films and to substrates, gas barrier properties against gases such as water vapor and oxygen, and ease of cutting when used in decorative boxes. Household wrap films are primarily used to store food in refrigerators or freezers, or to overlap when heating food in containers in a microwave oven.

[0003] Among the household wrap films currently on the market, those that are rated as the most user-friendly are those made primarily of polyvinylidene chloride resins. Other commercially available films, such as those made primarily of polyethylene resins, polypropylene resins, polyvinyl chloride resins, or poly-4-methylpentene-1 resins, are also available, but none of these have the adhesive strength of polyvinylidene chloride resin wrap films and are therefore inferior in terms of wrapping suitability, leading to the widespread use of vinylidene chloride wraps.

[0004] In recent years, the wrapping properties of household wrap films have required not only transparency and ease of cutting, but also firmness and resilience. They also need to be stable enough to withstand cooking in a microwave oven or other appliances, with minimal melting, perforation, significant deformation, or adhesion to the container, or deterioration of the film itself. They also need to adhere well to other wraps and to the container, especially when wrapping. In addition to good adhesion, consumers also strongly demand the opposing characteristic of easy removal of wrapped wrap film from a gift box.

[0005] As an example of a wrap film that satisfies such requirements, Patent Document 1 discloses a wrap film with an oxygen permeability of 110 cm 3 / m 2·day·atm at 23℃ or less, and the water vapor permeability is 20g / m 2 · day at 38℃, 90% RH or less, and the contact work X (mJ / 25cm 2 ) is 1.8≦X≦2.3, the crystal long period is 9.0 nm to 12.5 nm, and the film contains a copolymer consisting of 85 to 97 mass % vinylidene chloride monomer and 15 to 3 mass % vinyl chloride monomer.

[0006] Other examples of materials containing synthetic resin layers besides plastic wrap include tile carpet (TCP). Conventional roll carpets using the felt gripper method and foam-backed carpets make underfloor cable routing difficult and difficult to remove, resulting in poor maintenance. While the recently popular standard TCP backed with a synthetic resin layer improves maintenance, it is not expected to significantly reduce lightweight floor impact noise. Furthermore, for underfloor cable routing, double flooring for residential use currently resembles that for offices, and in many cases, TCP is installed as a surface layer on top of the double floor, resulting in complex and costly installation. While standard PVC-backed TCP with integrated cable storage grooves has been developed, it lacks soundproofing and cushioning properties. While some offer excellent cushioning, they are not well suited to underfloor cable routing. Furthermore, when considering maintenance at home, with TCP, dirty parts can be removed and washed in a separate location, but the currently mainstream size of 500mm square cannot be washed in a home washing machine.

[0007] As a TCP that solves these problems, for example, Patent Document 3 proposes a multifunctional TCP for residential use that has excellent soundproofing, cushioning, and shock absorption properties, is compatible with cable wiring, and is machine washable. Specifically, in a tile carpet having a backing material containing a back fabric layer formed under a surface fiber layer, a first synthetic resin layer, a glass fabric layer, a second synthetic resin layer, and latex impregnation are formed under the surface fiber layer, and the density is 0.05 to 0.15 g / cm.3 The proposed tile carpet is characterized in that a backing material consisting of a backing fabric layer with a thickness of 2 to 10 mm is laminated in layers, and the tile carpet is square with one side of 400 mm or less, and can be cut out by making an incision in at least the backing fabric portion. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Patent No. 7326208 [Patent Document 2] Patent No. 3258918 Summary of the Invention [Problem to be solved by the invention]

[0009] However, conventional wrap films, such as those made of vinyl chloride resins, do not have sufficient oxygen and water vapor barrier properties and tend to oxidize or dry out when food is stored, leaving room for improvement.

[0010] To solve the above problems, for example, a method of mixing vinyl chloride resin with vinylidene chloride resin, which has better barrier properties than vinyl chloride resin, has been considered. However, vinyl chloride resin and vinylidene chloride resin have low compatibility, making it difficult to mix the two uniformly. As a result, conventional wrap films made of vinyl chloride resin and vinylidene chloride resin tend to have poor surface smoothness (appearance).

[0011] Therefore, an object of the present invention is to provide a film that has a smooth surface, is aesthetically pleasing, and has an excellent effect of preserving the freshness of food. [Means for solving the problem]

[0012] As a result of extensive research, the present inventors have found that the above problems can be solved by producing a film that satisfies specific requirements, and have thus completed the present invention.

[0013] That is, the present invention relates to, for example, the following: [1] Oxygen permeability is 7000-120cm 3 / m 2 ·day·atm at 23℃, film. [2] Water vapor permeability: 500~30g / m 2 The film according to [1], wherein the temperature is 38°C and 90% RH. [3] The film according to [1] or [2], wherein the PVDC fraction index, expressed by the following formula (1), is 0.5 to 10.0 when the vinylidene chloride resin composition (PVDC) and the vinyl chloride resin composition (PVC) are observed 100 times by IR. PVDC fraction index = ((PVDC-derived peak area / (PVDC-derived peak area + PVC-derived peak area)) standard deviation) / ((PVDC-derived peak area / (PVDC-derived peak area + PVC-derived peak area)) average value) × 100 (1) [4] The film according to any one of [1] to [3], wherein the PVDC fraction index, expressed by the following formula (2), is 4.0 to 20.0 when a vinylidene chloride resin composition (PVDC) and a vinyl chloride resin composition (PVC) are observed 1600 times by Raman spectroscopy: PVDC fraction index = ((PVDC-derived peak area / (PVDC-derived peak area + PVC-derived peak area)) standard deviation) / ((PVDC-derived peak area / (PVDC-derived peak area + PVC-derived peak area)) average value) × 100 (2) [5] The film according to any one of [1] to [4], which has a thickness of 6 μm to 10 mm. [Effects of the Invention]

[0014] The film of the present invention has a smooth surface, is excellent in appearance, and is also excellent in the effect of preserving the freshness of food. [Brief explanation of the drawings]

[0015] [Figure 1]FIG. 1 is an example showing the portion of the peak area derived from PVDC and the portion of the peak area derived from PVC in an IR spectrum. [Figure 2] FIG. 2 is an example showing a portion of the peak area derived from PVDC and a portion of the peak area derived from PVC in a Raman spectrum. DETAILED DESCRIPTION OF THE INVENTION

[0016] Hereinafter, embodiments for carrying out the present invention (hereinafter abbreviated as "present embodiments") will be described in detail. The following embodiments are merely examples for explaining the present invention, and the present invention is not limited to these. In other words, the present invention can be carried out with any modifications within the scope of the gist thereof.

[0017] The film of this embodiment has an oxygen permeability of 7000 to 120 cm 3 / m 2 ·day·atm at 23°C. The film of this embodiment has an oxygen permeability in the above range, which results in a smooth surface, excellent aesthetics, and excellent food freshness preservation effect. From the same viewpoint, the film of this embodiment has an oxygen permeability of 4500 to 120 cm 3 / m 2 ·day·atm at 23℃ is preferable, and 2000~120cm 3 / m 2 ·day·atm at 23℃ is more preferable.

[0018] The method for controlling the oxygen permeability within the above range is not particularly limited, but an example thereof includes a method in which, when producing a film, a vinylidene chloride resin composition (PVDC) and a vinyl chloride resin composition (PVC) are first completely dissolved in tetrahydrofuran (THF), and then the mixed solution of the two is used as a raw material.

[0019] Although the mechanism by which the film of this embodiment exhibits the above-described effects is not clear, the present inventors speculate as follows. For example, it is believed that by uniformly mixing a vinylidene chloride resin composition (PVDC) and a vinyl chloride resin composition (PVC) when producing a film, the surface of the resulting film becomes smooth and has excellent aesthetic appearance. Furthermore, it is believed that by mixing a vinylidene chloride resin composition (PVDC), which has excellent barrier properties, with a vinyl chloride resin composition (PVC), the resulting film has improved barrier properties and is excellent in maintaining the freshness of food.

[0020] In this embodiment, the oxygen permeability can be measured by the method described in the Examples below.

[0021] The film of this embodiment has a water vapor permeability of 500 to 30 g / m 2 The film of this embodiment tends to have a better effect of preserving the freshness of food by having a water vapor transmission rate in the above range. From the same viewpoint, the film of this embodiment has a water vapor transmission rate of 350 to 30 cm 3 / m 2 ·day·atm at 23℃ is preferable, and 200-30cm 3 / m 2 ·day·atm at 23℃ is more preferable.

[0022] The method for controlling the water vapor permeability within the above range is not particularly limited, but an example thereof includes a method in which, when producing a film, a vinylidene chloride resin composition (PVDC) and a vinyl chloride resin composition (PVC) are first completely dissolved in tetrahydrofuran (THF), and then the mixed solution of the two is used as a raw material.

[0023] In this embodiment, the water vapor permeability can be measured by the method described in the examples below.

[0024] The film of the present embodiment preferably has a PVDC fraction index (hereinafter simply referred to as "PVDC fraction index by IR") expressed by the following formula (1) when a vinylidene chloride resin composition (PVDC) and a vinyl chloride resin composition (PVC) are observed 100 times by IR, of 0.5 to 10.0. PVDC fraction index = ((PVDC-derived peak area / (PVDC-derived peak area + PVC-derived peak area)) standard deviation) / ((PVDC-derived peak area / (PVDC-derived peak area + PVC-derived peak area)) average value) × 100 (1) The film of this embodiment, having a PVDC fraction index in IR within the above range, tends to have a smooth surface and better aesthetic appearance, and also tends to be better at preserving the freshness of food. From the same viewpoint, the film of this embodiment more preferably has a PVDC fraction index in IR of 4.0 to 0.5, and even more preferably 1.5 to 0.5.

[0025] The method for controlling the PVDC fraction index in IR to fall within the above range is not particularly limited, but an example thereof includes a method in which, when producing a film, a vinylidene chloride resin composition (PVDC) and a vinyl chloride resin composition (PVC) are first completely dissolved in tetrahydrofuran (THF), and then the resulting mixture is used as a raw material.

[0026] In the present embodiment, the PVDC-derived peak area in formula (1) is the area of ​​the peak at 1025 cm in the IR spectrum of the film. -1 and 1085cm -1 The baseline is drawn by connecting the line at 1025 cm and the IR spectrum. -1 and 1085cm -1 The area of ​​the black portion surrounded by the IR spectrum and the baseline connecting the lines 1 and 2 is the area of ​​the peak derived from PVDC in formula (1). In this embodiment, the area of ​​the peak derived from PVC in formula (1) is the area of ​​the peak derived from PVC at 1215 cm in the IR spectrum of the film. -1 and 1290cm-1 The baseline is drawn by connecting the line and the IR spectrum. Specifically, for example, in the IR spectrum of the film shown in the upper part of Figure 1, the IR spectrum of the film at 1215 cm -1 and 1290cm -1 The area of ​​the black portion surrounded by the IR spectrum and the baseline connecting these points with a straight line is the area of ​​the peak derived from PVC in formula (1). In this embodiment, the PVDC fraction index in IR can be specifically measured by the method described in the Examples below.

[0027] The film of the present embodiment preferably has a PVDC fraction index (hereinafter simply referred to as "Raman PVDC fraction index") of 4.0 to 20.0, which is expressed by the following formula (2) when a vinylidene chloride resin composition (PVDC) and a vinyl chloride resin composition (PVC) are observed 1600 times by Raman spectroscopy. PVDC fraction index = ((PVDC-derived peak area / (PVDC-derived peak area + PVC-derived peak area)) standard deviation) / ((PVDC-derived peak area / (PVDC-derived peak area + PVC-derived peak area)) average value) × 100 (2) The film of this embodiment, having a PVDC fraction index by Raman spectroscopy within the above range, tends to have a smoother surface, more aesthetically pleasing appearance, and more effective in preserving the freshness of food. From the same viewpoint, the film of this embodiment preferably has a PVDC fraction index by Raman spectroscopy of 11.0 to 20.0, more preferably 14.7 to 20.0.

[0028] The method for controlling the PVDC fraction index by Raman spectroscopy within the above range is not particularly limited, but an example thereof includes a method in which, when producing a film, a vinylidene chloride resin composition (PVDC) and a vinyl chloride resin composition (PVC) are first completely dissolved in tetrahydrofuran (THF), and then the resulting mixture is used as a raw material.

[0029] In this embodiment, the peak area derived from PVDC in formula (2) is 405 to 450 cm -1 and 467-495cm -1 The baseline is drawn by connecting two wavenumber points where the signal intensity is at its minimum within the range of 405 cm. -1 and 450cm -1 The area of ​​the black portion surrounded by the baseline connecting the lines and the Raman spectrum is the area of ​​the peak derived from PVDC in formula (2). In this embodiment, the area of ​​the peak derived from PVC in formula (2) is the area of ​​the peak derived from 1380 to 1405 cm -1 and 1465~1495cm -1 A baseline is drawn by connecting two wavenumber points where the intensity is at a minimum in the range of 1380 to 1405 cm. The area enclosed by the baseline and the Raman spectrum is defined as the area. Specifically, for example, in the Raman spectrum shown in the upper part of Figure 2, -1 and 1465~1495cm -1 A baseline is drawn by connecting the two wavenumbers where the intensity is at its minimum within this range with a straight line, and the area of ​​the black part enclosed by this baseline and the Raman spectrum is the area of ​​the PVC-derived peak in formula (2). In this embodiment, the PVDC fraction index in Raman can be specifically measured by the method described in the examples below.

[0030] The film of this embodiment preferably has a thickness of 6 μm to 10 mm. When the film of this embodiment has a thickness within this range, it tends to be easier to wrap food. From the same viewpoint, the film of this embodiment more preferably has a thickness of 6 μm to 5 mm, and even more preferably 6 μm to 7 μm.

[0031] [Film components] The film of the present embodiment preferably contains a vinylidene chloride resin composition (PVDC) and a vinyl chloride resin composition (PVC). In the film of this embodiment, the content of the vinylidene chloride resin composition (PVDC) is preferably 5 to 95 wt%, more preferably 15 to 95 wt%, and even more preferably 40 to 95 wt%. Furthermore, in the film of this embodiment, the content of the vinyl chloride resin composition (PVC) is preferably 5 to 95 wt%, more preferably 5 to 85 wt%, and even more preferably 5 to 60 wt%. When the contents of the vinylidene chloride resin composition (PVDC) and the vinyl chloride resin composition (PVC) are within the above ranges, the film of this embodiment tends to have an excellent effect of preserving the freshness of food.

[0032] The film of the present embodiment may contain other polymers capable of forming a film in addition to the vinylidene chloride resin composition (PVDC) and the vinyl chloride resin composition (PVC).

[0033] Suitable examples of other polymers capable of forming a film include olefin resins, ester resins, and amide resins. Examples of olefin resins include, but are not limited to, polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and copolymers based on these. Examples of ester resins include, but are not limited to, polyethylene terephthalate, polypropylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-2,6-naphthalate, polylactic acid, and polyhydroxyglycolic acid. Examples of amide resins include, but are not limited to, nylon 6, nylon 7, nylon 66, nylon 610, nylon 612, nylon 46, and nylon 6T.

[0034] The vinylidene chloride resin composition contained in the film of this embodiment may be a homopolymer of a vinylidene chloride monomer or a copolymer of a vinylidene chloride monomer and a monomer copolymerizable therewith. The vinylidene chloride resin composition may contain one type of vinylidene chloride resin or two or more types of vinylidene chloride resins.

[0035] The vinylidene chloride resin composition contained in the film of the present embodiment may be a petroleum-derived resin or a plant-derived resin.

[0036] The monomer copolymerizable with vinylidene chloride monomer is not particularly limited, and examples thereof include vinyl chloride, acrylic acid esters such as methyl acrylate and butyl acrylate, methacrylic acid esters such as methyl methacrylate and butyl methacrylate, acrylonitrile, vinyl acetate, etc. Among these, vinyl chloride is preferred from the viewpoints of easily achieving a balance between oxygen / water barrier properties and extrusion processability and also having excellent film adhesion. These may be used alone or in combination of two or more.

[0037] When a copolymer of vinylidene chloride monomer and the above-mentioned monomers is used, it is preferable that the copolymer is composed of 85 to 97 mass% vinylidene chloride monomer and 15 to 3 mass% of a monomer copolymerizable therewith, from the viewpoints of crystallinity, processability, film properties, etc. By making the vinylidene chloride monomer ratio 85 mass% or more, it is possible to further improve the oxygen / water barrier properties and film cuttability, and by making the vinylidene chloride monomer ratio 97 mass% or less, it is possible to further improve the processability. The monomer ratio was measured using an FX-270 (manufactured by JEOL Ltd.) using d-THF as a solvent. 1 The value was calculated from the integral ratio of the peaks derived from each monomer component in the H-NMR spectrum.

[0038] The vinyl chloride resin composition contained in the film of this embodiment may be a homopolymer of a vinyl chloride monomer or a copolymer of a vinyl chloride monomer and a monomer copolymerizable therewith. The vinyl chloride resin composition may contain one type of vinyl chloride resin or two or more types of vinyl chloride resins.

[0039] The vinyl chloride resin composition contained in the film of the present embodiment may be a petroleum-derived resin or a plant-derived resin.

[0040] The polyvinyl chloride resin may be a vinyl chloride homopolymer (polyvinyl chloride resin) from the viewpoint of excellent mechanical properties, or may be a copolymer of vinyl chloride and other monomers copolymerizable therewith from the viewpoint of imparting other properties. The copolymer may be a graft copolymer, a block copolymer, or a random copolymer. Examples of other monomers include olefins such as vinylidene chloride, ethylene, propylene, and butene; vinyl esters of saturated acids such as vinyl acetate and vinyl laurate; alkyl esters of unsaturated acids such as methyl acrylate and methyl methacrylate; alkyl vinyl ethers such as lauryl vinyl ether; aromatic vinyl compounds such as maleic acid, acrylonitrile, styrene, and α-methylstyrene; α-olefin monomers such as 1-hexene; ester monomers such as vinyl propionate; ether monomers such as butyl vinyl ether, cetyl vinyl ether, and phenyl vinyl ether; cyanide vinyl compounds such as (meth)acrylonitrile; halogenated vinyl compounds such as vinyl fluoride; acrylic acid esters such as methyl acrylate, ethyl acrylate, and butyl acrylate; and similarly substituted methacrylic acid esters. acrylic acids such as acrylic acid and methacrylic acid; N-substituted maleimide monomers such as N-phenylmaleimide and N-methylmaleimide; methylstyrene; and vinylidene fluoride.

[0041] When the polyvinyl chloride resin is a copolymer, the content of vinyl chloride units in the copolymer may be 10% by mass or more, based on the total amount of monomer units, and from the viewpoint of excellent mechanical properties, is preferably 30% by mass or more, more preferably 50% by mass or more. The upper limit of the content of vinyl chloride units in the copolymer is not particularly limited, and may be, for example, 99% by mass or less, based on the total amount of monomer units.

[0042] The vinylidene chloride resin composition and / or vinyl chloride resin composition may contain additives such as known plasticizers and stabilizers. The plasticizer is not particularly limited, and known ones can be used. Examples include acetyl tributyl citrate, acetylated monoglyceride, and dibutyl sebacate. The stabilizer is not particularly limited, and known ones can be used. Examples include epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil.

[0043] In addition, known weather resistance improvers, antibacterial agents, antifogging agents, heat stabilizers, light stabilizers, lubricants, fillers, plate-out inhibitors, antioxidants, mold release agents, viscosity reducers, surfactants, colorants, fluorescent agents, surface treatment agents, crosslinking agents, processing aids, adhesives, antistatic agents, UV absorbers, antiblocking agents, oligomers such as polyester, MBS (methyl methacrylate-butadiene-styrene), etc., used in food packaging materials may also be added, provided that the effects of this embodiment are not impaired. The weather resistance improvers are not particularly limited, and known ones can be used. Examples include UV absorbers such as 2-(2'-hydroxy-3'5'-di-tert-butylphenyl)-5-chlorobenzotriazole. The antifogging agents are not particularly limited, and known ones can be used. Examples include surfactants such as glycerin fatty acid esters, diglycerin fatty acid esters, and sorbitan fatty acid esters. The antibacterial agents are not particularly limited, and known ones can be used. For example, natural antibacterial agents such as grapefruit seed extract and moso bamboo extract can be mentioned.

[0044] The film of this embodiment does not necessarily have to be a single-layer film. In the case of a multilayer structure, the layer that contacts the container may be composed of two or more layers, as long as it is mainly composed of a crystalline polymer and contains a liquid component, and the practical adhesion is unchanged. This multilayer structure may include a glass sheet layer for shape stabilization and a surface protective layer. The surface protective layer may include a cured product of an ionizing radiation-curable resin composition.

[0045] The film of this embodiment may contain a liquid component.

[0046] The liquid component that is preferably used varies depending on the type of polymer, and from the viewpoint of imparting flexibility to the film, for example, in the case of an aliphatic hydrocarbon polymer, a liquid component having an alkyl group or a methylene chain moiety is preferably used, and in the case of an ester-based polymer or an amide-based polymer, a liquid component having a functional group capable of hydrogen bonding, such as a carbonyl group, an ether group, or a hydroxyl group, is preferably used.

[0047] For example, those having an alkyl group include mineral oil, liquid paraffin, saturated hydrocarbon compounds, etc. Those containing a functional group capable of forming a hydrogen bond, such as a carbonyl group, an ether group, or a hydroxyl group, include aliphatic alcohols, alicyclic alcohols, polyhydric alcohols thereof, esters of the above-mentioned alcohol components with aliphatic or aromatic (polyvalent) carboxylic acids, esters of aliphatic hydroxycarboxylic acids with alcohols and / or fatty acids, modified products of these esters, and polyoxyethylene alkyl ethers and / or esters thereof. More specifically, examples of suitable materials include polyglycerols such as glycerin, diglycerin, triglycerin, and tetraglycerin, and the like, which are used as the starting material for the alcohol component and, as the acid component, mono-, di-, and triesters, polyesters, etc., of fatty acids such as lauric acid, palmitic acid, stearic acid, oleic acid, and linoleic acid, or esters of sorbitan and the above fatty acids, or esters of ethylene glycol, propylene glycol, tetramethylene glycol, and condensates thereof with the above fatty acids, or esters of aliphatic hydroxycarboxylic acids such as citric acid, malic acid, and tartaric acid with lower alcohols having 10 or less carbon atoms, or esters of polycarboxylic acids such as malonic acid, succinic acid, glutaric acid, and adipic acid with aliphatic alcohols, or modified products of these esters such as epoxidized soybean oil and epoxidized linseed oil. In particular, when used as a food packaging wrap, liquid components that are food additives as defined by the Food Sanitation Act are preferably used. Furthermore, from the standpoint of heat resistance, liquid components with a boiling point of 200°C or higher are preferably used.

[0048] Next, a method for producing a molded article will be described as an example of a method for producing a film of this embodiment. For example, various methods can be used to produce a molded article, but in the method for producing a film of this embodiment, a vinylidene chloride resin composition and a vinyl chloride resin composition are first completely dissolved in tetrahydrofuran (THF), and then the mixed solution of the two is used as a raw material. This allows the oxygen permeability of the film of this embodiment to be controlled within the above-mentioned range. An example of a method and conditions for producing a molded body will be specifically described below. 1) Preparation of solutions For example, commercially available Saran Wrap (registered trademark) (Asahi Kasei Home Products Corporation) is used as the vinyl chloride resin composition. Furthermore, commercially available Riken Wrap (registered trademark) (Riken Technos Corporation) is used as the vinyl chloride resin composition. The two components are pre-prepared to achieve a predetermined weight fraction, so that the total sample weight is 5.00 g. 50 mL of solvent measured with a measuring cylinder is added to this. Then, a solution of the sample (solution sample) is prepared using a 50°C water bath and an ultrasonic cleaner. 2) Preparation of molded body samples The solution sample obtained above was coated (applied) onto aluminum foil a predetermined number of times using a Mayer bar and dried in an inert oven at 80°C for 15 seconds under a nitrogen flow of 10 L / min. After coating and drying in this manner, the obtained film was peeled off from the aluminum foil to prepare a molded body. The thickness of the prepared molded body was measured at 10 random points using a dial gauge, and the average of the measured values ​​was calculated.

[0049] The above description is one example of the method for producing the film of this embodiment, and the method may be carried out using various apparatus configurations and conditions other than those described above, and for example, other known methods may be employed.

[0050] The film of the present embodiment is not particularly limited, but examples thereof include wrap films, flooring materials, and building materials, with wrap films and flooring materials being preferred.

[0051] The above-described embodiments are intended to facilitate understanding of the present invention and are not intended to limit the present invention. The elements of the embodiments, as well as their arrangement, materials, conditions, shapes, sizes, etc., are not limited to those illustrated and can be modified as appropriate. Furthermore, configurations shown in different embodiments can be partially substituted or combined with each other. [Example]

[0052] The features of the present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto. That is, the materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Furthermore, the values ​​of various production conditions and evaluation results in the following examples represent preferred upper or lower limits in the embodiments of the present invention, and preferred ranges may be defined by combining the above-mentioned upper or lower limits with the values ​​of the following examples or values ​​between the examples.

[0053] The measurement and evaluation methods used in the examples and comparative examples are as follows.

[0054] (1) Oxygen permeability Oxygen permeability was measured using a MOCON OX TRAN 2 / 21MH (trade name) according to ASTM D3985. The sample was placed in the device and the value measured 4 hours later was used. Measurements were carried out at 23°C. The lower the oxygen permeability, the higher the oxygen barrier properties.

[0055] (2) Water vapor permeability The water vapor permeability was measured using PERMATRAN W-398 (trade name) manufactured by MOCON, with reference to ASTM F1249. The value measured 3 hours after placing the sample in the device was used. Measurements were performed under conditions of 38°C and 90% RH. The lower the water vapor permeability, the higher the water barrier properties.

[0056] (3) PVDC fraction index in IR The PVDC fraction index of the molded articles (films) obtained in the examples and comparative examples described below was measured by IR as follows. (Measurement equipment and conditions) The conditions for micro-IR mapping were as follows: Instrument: Varian 670-IR / 620-IR Measurement method: Microscopic IR transmission method Detector MCT Resolution 4cm-1 Total number of times: 64 Aperture 20μm Measurement range: 200 μm square (spectral processing) All measured spectra were processed using the software provided with the instrument, ResolutionsPro Version 5.2.0 manufactured by Agilent Technologies. (IR measurement conditions) A resolution of 4cm was measured by the transmission method using a microscopic IR measurement device. -1 The aperture was set to 20 μm, and measurements were taken at a total of 100 points in 10 rows and columns, mapping an area of ​​200 μm square. (Spectral analysis method) The PVDC fraction index in IR was the value expressed by the following formula (1) when 100 observations were made in the above IR measurement. PVDC fraction index = ((PVDC-derived peak area / (PVDC-derived peak area + PVC-derived peak area)) standard deviation) / ((PVDC-derived peak area / (PVDC-derived peak area + PVC-derived peak area)) average value) × 100 (1) However, the peak area derived from PVDC is 1025 cm -1 From 1085cm -1 A straight line was drawn at the baseline, and the area enclosed by the baseline and the IR spectrum was defined as the peak area derived from PVC. -1 From 1290cm -1 A straight line was drawn as a baseline, and the area enclosed by the baseline and the IR spectrum was defined as the area. For the 100 measured IR spectra, (PVDC-derived peak area / (PVDC-derived peak area+PVC-derived peak area) was calculated. From the calculated values, the average value and standard error of 100 measurements were calculated, and the PVDC fraction index was calculated using the above formula (1).

[0057] (2) PVDC fraction index by Raman The PVDC fraction index of the molded articles (films) obtained in the examples and comparative examples described below was measured by Raman spectroscopy as follows. (Raman measurement conditions) The conditions for microscopic Raman imaging are as follows: Equipment: Renishaw In Via Reflex Laser wavelength 532nm Laser power: 10 or 50% (1.8 or 9.0 mW at the sample position, respectively) Objective lens 100x Exposure time: 1 s Accumulation count: 1 time Incident polarized light Circularly polarized light Analyzer λ / 4 plate Laser shape line (Stream line) Measurement range: 25 μm square Approximately 2000 measurement points However, only PVC / PVDC=90 / 10 is 1600 points (spectral processing) All measured spectra were subjected to (i) baseline correction, (ii) cosmic ray removal, and (iii) noise removal using a noise filter. These processes were performed using the software provided with the instrument, Renishaw Wire Version 4.1. For (i) baseline correction, an algorithm called intelligent baseline correction was used. For (iii) noise filtering, the spectrum was reconstructed up to the number of components where peaks were observed, and noise components were removed. (Raman measurement conditions) Imaging measurements were performed at over 1000 points at 0.6 μm intervals using a Raman spectrometer. The objective lens was 100x, NA=0.9, and the polarization state of the laser light incident on the sample using the confocal optical system was circularly polarized using a λ / 4 plate. Furthermore, measurements were performed with a λ / 4 plate placed in front of the spectrometer slit. The grating was 1800 l / mm 2 was used. (Spectral analysis method) All spectra were subjected to baseline correction, cosmic ray removal, and noise filtering to improve the signal-to-noise ratio. The PVDC fraction index in Raman was calculated as the value expressed by the following formula (2) after 1600 observations using the above Raman spectrum. PVDC fraction index = ((PVDC-derived peak area / (PVDC-derived peak area + PVC-derived peak area)) standard deviation) / ((PVDC-derived peak area / (PVDC-derived peak area + PVC-derived peak area)) average value) × 100 (2) However, the PVDC-derived peak area is the area between 405 and 450 cm -1 and 467-495cm -1 The baseline was determined by connecting the two wavenumbers where the signal intensity was at its minimum in the range of 1380 to 1405 cm. The area enclosed by the baseline and the Raman spectrum was defined as the area of ​​the PVC-derived peak. -1 and 1465~1495cm -1 A baseline was drawn by connecting two wavenumber points where the intensity was at its minimum within the range of 1 / 2, and the area enclosed by the baseline and the Raman spectrum was defined as the area. For the 1600 points measured in the Raman spectrum, (PVDC-derived peak area / (PVDC-derived peak area+PVC-derived peak area)) was calculated. From the calculated values, the average value and standard error of 1600 measurements were calculated, and the PVDC fraction index was calculated according to the above formula (2).

[0058] (4) Measuring film thickness The thickness of the molded body (film) was measured using a precision dial gauge (TM-1201, manufactured by Teclock Corporation) in an atmosphere of 23±2°C and 50±10% RH. The thickness of the molded body was measured at 10 random points using the dial gauge, and the average of the measured values ​​was calculated to be the film thickness.

[0059] (5) Maintaining the freshness of food The molded articles (films) obtained in the examples and comparative examples were stored at 23±2°C and 50±10% RH for 24 hours. After storage, the molded articles were used to wrap halved avocados and were subjected to a sensory evaluation of their freshness-preserving effect. The sensory evaluation was carried out by the following method. Ten experienced evaluators (including both men and women) cut the molded product into 22cm x 22cm pieces, wrapped an avocado in it, and stored it at 23±2°C and 50±10% RH for 24 hours. Afterwards, the freshness-keeping effect was evaluated on a scale of 0 to 10 (10 being an excellent freshness-keeping effect, 0 being a poor freshness-keeping effect). 10 points: Excellent freshness retention effect. 8 points: Excellent freshness retention effect. 6 points: Fairly good freshness retention effect. 4 points: The freshness preservation effect is not very good. 2 points: The freshness preservation effect is not good. 0 points: The freshness preservation effect is not very good. The freshness-preserving effect of the molded product was evaluated based on the average scores of 10 evaluators and according to the following evaluation criteria. If the freshness preservation effect is rated "A", the molded product has an exceptionally excellent freshness preservation effect, and can be said to have the best freshness preservation effect. If the rating is "B", the molded product can be said to have an excellent freshness preservation effect. If the rating is "C", the molded product can be said to have a good freshness preservation effect. If the rating is "D", the molded product does not have a very good freshness preservation effect. [Evaluation criteria] A: 8.0 points or more B: 6.0 points or more and less than 8.0 points C: 4.0 points or more and less than 6.0 points D: Less than 4.0 points

[0060] (6) Surface smoothness of recycled materials (aesthetics) The molded articles (films) obtained in the examples and comparative examples were stored at 23±2°C and 50±10% RH for 24 hours. After storage, the molded articles were evaluated for surface smoothness. Sensory evaluation was carried out by the following method. That is, 10 experienced evaluators (including both men and women) cut the molded products into 22 cm x 22 cm pieces, attached them to glass plates, and stored them for 24 hours at 23±2°C and 50±10% RH. After that, the surface smoothness was evaluated on a scale of 0 to 10 in 2-point increments (10 being very good surface smoothness, 0 being poor surface smoothness) as follows: 10 points: The surface is extremely smooth. 8 points: Excellent surface smoothness. 6 points: The surface is fairly smooth. 4 points: The surface is not very smooth. 2 points: The surface is not smooth. 0 points: The surface is not very smooth. The surface smoothness of the molded body was evaluated based on the average scores of 10 evaluators and in accordance with the following evaluation criteria. If the freshness preservation effect is evaluated as "good", the molded product has excellent aesthetic appearance, and if it is evaluated as "poor", the molded product has poor aesthetic appearance. [Evaluation criteria] ○: 5.0 points or more (Excellent aesthetics) ×: Less than 5.0 points (poor aesthetics).

[0061] [Example 1] 1) Preparation of solutions Commercially available Saran Wrap (registered trademark) (Asahi Kasei Home Products Corporation) was used as the vinylidene chloride resin composition, and it was pulverized to 0.50 g. Commercially available Riken Wrap (registered trademark) (Riken Technos Corporation) was used as the vinyl chloride resin composition, and it was pulverized to 4.50 g. The two were mixed to prepare a sample weighing 5.00 g in total. 50 mL of tetrahydrofuran (hereinafter also referred to as "THF") measured with a measuring cylinder was added to this. Then, a THF solution of the sample (solution sample) was prepared using a water bath at 50°C and an ultrasonic cleaner. 2) Preparation of molded body samples The solution sample prepared above was coated (applied) onto aluminum foil using a Mayer bar a predetermined number of times to a thickness of 6 μm, and then dried in an inert oven at 80°C for 15 seconds under a nitrogen flow of 10 L / min. After coating and drying, the resulting film was peeled off from the aluminum foil to produce a molded product (film).

[0062] [Example 2] As the vinylidene chloride resin composition, commercially available Saran Wrap (registered trademark) (Asahi Kasei Home Products Corporation) was used and pulverized to 1.25 g. As the vinyl chloride resin composition, commercially available Riken Wrap (registered trademark) (Riken Technos Corporation) was used and pulverized to 3.75 g. The two were mixed together to prepare a sample weighing 5.00 g in total. A molded body (film) was produced in the same manner as in Example 1 except for the above.

[0063] [Example 3] As the vinylidene chloride resin composition, commercially available Saran Wrap (registered trademark) (Asahi Kasei Home Products Corporation) was used and pulverized to 2.50 g. As the vinyl chloride resin composition, commercially available Riken Wrap (registered trademark) (Riken Technos Corporation) was used and pulverized to 2.50 g. The two were mixed together to prepare a sample weighing 5.00 g in total. A molded body (film) was produced in the same manner as in Example 1 except for the above.

[0064] [Example 4] A molded body (film) was produced in the same manner as in Example 1, except that coating was performed a predetermined number of times so that the thickness of the molded body (film) became 8 μm.

[0065] [Example 5] As the vinylidene chloride resin composition, commercially available Saran Wrap (registered trademark) (Asahi Kasei Home Products Corporation) was used and pulverized to 1.25 g. As the vinyl chloride resin composition, commercially available Riken Wrap (registered trademark) (Riken Technos Corporation) was used and pulverized to 3.75 g. The two were mixed together to prepare a sample weighing 5.00 g in total. A molded body (film) was produced in the same manner as in Example 4 except for the above.

[0066] [Example 6] As the vinylidene chloride resin composition, commercially available Saran Wrap (registered trademark) (Asahi Kasei Home Products Corporation) was used and pulverized to 2.50 g. As the vinyl chloride resin composition, commercially available Riken Wrap (registered trademark) (Riken Technos Corporation) was used and pulverized to 2.50 g. The two were mixed together to prepare a sample weighing 5.00 g in total. A molded body (film) was produced in the same manner as in Example 4 except for the above.

[0067] [Example 7] A molded body (film) was produced in the same manner as in Example 1, except that coating was performed a predetermined number of times so that the thickness of the molded body (film) became 10 mm (10,000 μm).

[0068] [Example 8] As the vinylidene chloride resin composition, commercially available Saran Wrap (registered trademark) (Asahi Kasei Home Products Corporation) was used and pulverized to 1.25 g. As the vinyl chloride resin composition, commercially available Riken Wrap (registered trademark) (Riken Technos Corporation) was used and pulverized to 3.75 g. The two were mixed together to prepare a sample weighing 5.00 g in total. A molded body (film) was produced in the same manner as in Example 7 except for the above.

[0069] [Example 9] As the vinylidene chloride resin composition, commercially available Saran Wrap (registered trademark) (Asahi Kasei Home Products Corporation) was used and pulverized to 2.50 g. As the vinyl chloride resin composition, commercially available Riken Wrap (registered trademark) (Riken Technos Corporation) was used and pulverized to 2.50 g. The two were mixed and prepared in advance so that the total sample weight was 5.00 g. A molded body (film) was produced in the same manner as in Example 7 except for the above.

[0070] [Comparative Example 1] As the vinyl chloride resin composition, commercially available Rikenwrap (registered trademark) (Riken Technos Corporation) was used and pulverized to 5.00 g. The two were mixed together to prepare a sample weighing 5.00 g in total. Otherwise, a molded body (film) was produced in the same manner as in Example 1.

[0071] Comparative Example 2 A molded body (film) was produced in the same manner as in Example 1, except that dimethylformamide (DMF) was used as the solution.

[0072] Comparative Example 3 A molded article (film) was produced in the same manner as in Example 2, except that dimethylformamide (DMF) was used as the solution.

[0073] Comparative Example 4 A molded body (film) was produced in the same manner as in Example 3, except that dimethylformamide (DMF) was used as the solution.

[0074] Comparative Example 5 A molded body (film) was produced in the same manner as in Comparative Example 1, except that coating was performed a predetermined number of times so that the thickness of the molded body (film) became 8 μm.

[0075] Comparative Example 6 A molded body (film) was produced in the same manner as in Comparative Example 2, except that coating was performed a predetermined number of times so that the thickness of the molded body (film) became 8 μm.

[0076] Comparative Example 7 A molded body (film) was produced in the same manner as in Comparative Example 3, except that coating was performed a predetermined number of times so that the thickness of the molded body (film) became 8 μm.

[0077] [Comparative Example 8] A molded body (film) was produced in the same manner as in Comparative Example 4, except that coating was performed a predetermined number of times so that the thickness of the molded body (film) became 8 μm.

[0078] Comparative Example 9 A molded body (film) was produced in the same manner as in Comparative Example 1, except that coating was performed a predetermined number of times so that the thickness of the molded body (film) became 10 mm (10,000 μm).

[0079] [Comparative Example 10] A molded body (film) was produced in the same manner as in Comparative Example 2, except that coating was performed a predetermined number of times so that the thickness of the molded body (film) became 10 mm (10,000 μm).

[0080] [Comparative Example 11] A molded body (film) was produced in the same manner as in Comparative Example 3, except that coating was performed a predetermined number of times so that the thickness of the molded body (film) became 10 mm (10,000 μm).

[0081] [Comparative Example 12] A molded body (film) was produced in the same manner as in Comparative Example 4, except that coating was performed a predetermined number of times so that the thickness of the molded body (film) became 10 mm (10,000 μm).

[0082] [Table 1]

[0083] [Table 2]

[0084] [Table 3]

Claims

1. Oxygen permeability is 7000 to 120 cm 3 / m 2 ·day·atm at 23°C, film.

2. Water vapor permeability: 500 to 30 g / m 2 The film according to claim 1, wherein the film is maintained at 38°C and 90% RH for one day.

3. 3. The film according to claim 1, wherein the PVDC fraction index, expressed by the following formula (1), is 0.5 to 10.0 when the vinylidene chloride resin composition (PVDC) and the vinyl chloride resin composition (PVC) are observed 100 times by IR. PVDC fraction index=((PVDC-derived peak area / (PVDC-derived peak area+PVC-derived peak area)) standard deviation) / ((PVDC-derived peak area / (PVDC-derived peak area+PVC-derived peak area)) average value)×100 (1)

4. 3. The film according to claim 1, wherein the PVDC fraction index, expressed by the following formula (2), is 4.0 to 20.0 when the vinylidene chloride resin composition (PVDC) and the vinyl chloride resin composition (PVC) are observed 1,600 times by Raman spectroscopy: PVDC fraction index=((PVDC-derived peak area / (PVDC-derived peak area+PVC-derived peak area)) standard deviation) / ((PVDC-derived peak area / (PVDC-derived peak area+PVC-derived peak area)) average value)×100 (2)

5. 3. The film according to claim 1, having a thickness of 6 μm to 10 mm.

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