film

Abstract

To provide a film that has a smooth surface, is excellent in appearance, and can suppress rust from occurring on facilities (such as piping) during high-temperature treatment in recycling.SOLUTION: In a film, the PVDC fraction index, expressed by the following formula (1), of a vinylidene chloride resin composition (PVDC) and a vinyl chloride resin composition (PVC) is 0.5 to 10.0 when 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)SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] In recent years, in view of environmental and waste problems, there has been a worldwide increase in demand for the recovery and reuse of materials consumed in the market, so-called recycling. In recycling, for example, a process is generally adopted in which recovered materials are cut, sorted and washed as necessary, and then subjected to high-temperature treatment using an extruder or the like.

[0003] Various methods have been proposed for processing recycled materials. For example, Patent Document 1 proposes a method for processing waste plastics that allows for the production of high-quality recycled pellets from composite plastic materials without using a compatibilizer. Specifically, the proposed method includes the steps of pretreating waste plastics made of a laminated film formed from two or more thermoplastic resin layers with different melting points, adding pressurized saturated steam to the pretreated material obtained in the pretreatment step and melting it while mixing, and pelletizing the molten material obtained in the melting while mixing step.

[0004] Another example of a recyclable material is a film. Among films, for example, wrap film is used in many ordinary households as a wrap film for food and the like because it has excellent properties such as adhesion to other films and to adherends, gas barrier properties against gases such as water vapor and oxygen, and ease of cutting when used in a decorative box. Household wrap film is mainly used to store food in a refrigerator or freezer, or to overlap when heating food in a container in a microwave oven.

[0005] Among the currently commercially available household wrap films, those that are rated as the most user-friendly are those made primarily of vinylidene chloride resins. Other commercially available films include those made primarily of ethylene resins, propylene resins, vinyl chloride resins, or 4-methylpentene-1 resins, but none of these have the adhesive properties of vinylidene chloride resin wrap films and are therefore inferior in terms of wrapping suitability, leading to the widespread use of vinylidene chloride wraps.

[0006] 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.

[0007] As an example of a wrap film that satisfies such requirements, Patent Document 2 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.

[0008] Other recyclable materials include carpet tiles (TCP). Conventional roll carpets using the felt gripper method and carpets backed with foam 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, considering home maintenance, while TCP allows for the soiled sections to be removed and washed separately, the currently mainstream 500mm square size cannot be washed in a household washing machine.

[0009] 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]

[0010] [Patent Document 1] Japanese Patent Application Publication No. 2023-138456 [Patent Document 2] Patent No. 7326208 [Patent Document 3] Patent No. 3258918 Summary of the Invention [Problem to be solved by the invention]

[0011] However, conventional molded articles, such as wrap films made of vinylidene chloride resins, are difficult to recycle. Specifically, vinylidene chloride resins are more susceptible to dehydrochlorination than vinyl chloride resins, and when a molded sheet is crushed and recycled, the dehydrochlorination proceeds at high temperatures, which tends to corrode piping and other equipment, making recycling difficult.

[0012] Therefore, even if attempts are made to utilize vinylidene chloride-based molded articles as recycled materials to achieve resource circulation, molding recycled materials is difficult, making it difficult to achieve resource circulation.

[0013] To solve the above problems, for example, a method of mixing a vinyl chloride resin, which is difficult to dehydrochlorinate, with a vinylidene chloride resin is conceivable, but 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).

[0014] Therefore, an object of the present invention is to provide a film that has a smooth surface, is excellent in appearance, and is less likely to cause rust in equipment (such as piping) during high-temperature treatment during recycling. [Means for solving the problem]

[0015] 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.

[0016] That is, the present invention relates to, for example, the following: [1] A film in which the PVDC fraction index, expressed by the following formula (1), of a vinylidene chloride resin composition (PVDC) and a vinyl chloride resin composition (PVC) is 0.5 to 10.0 when 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) [2] The film according to [1], wherein the PVDC fraction index, expressed by the following formula (2), of a vinylidene chloride resin composition (PVDC) and a vinyl chloride resin composition (PVC) is 4.0 to 20.0 when 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) [3] The film according to [1] or [2], wherein, when measured by thermogravimetric analysis in an air atmosphere by scanning from room temperature to 1000°C at a heating rate of 10°C / min, the weight loss at 270°C is 40% by weight or less, the weight loss at 260°C is 35% by weight or less, and the weight loss at 250°C is 30% by weight or less. [4] The film according to any one of [1] to [3], which has a thickness of 6 μm to 10 mm. [Effects of the Invention]

[0017] The film of the present invention has a smooth surface, is excellent in appearance, and is less likely to cause rust in equipment (such as piping) during high-temperature treatment during recycling. [Brief explanation of the drawings]

[0018] [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

[0019] 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.

[0020] The film of the present embodiment has a PVDC fraction index (hereinafter simply referred to as "PVDC fraction index by IR") expressed by the following formula (1) when observed 100 times by IR of a vinylidene chloride resin composition (PVDC) and a vinyl chloride resin composition (PVC), 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 has these characteristics, resulting in a smooth surface, excellent aesthetics, and less rust on equipment (such as piping) during high-temperature treatment during recycling. From the same viewpoint, the PVDC fraction index of the film of this embodiment in IR is more preferably 2.0 to 10.0, and even more preferably 4.0 to 10.0.

[0021] 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.

[0022] 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) during film production, 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) with a vinyl chloride resin composition (PVC), the resulting film can be imparted with a dehydrochlorination inhibitory effect, which in turn makes it less likely for equipment (such as piping) to rust during high-temperature treatment during recycling.

[0023] 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 -1The area of ​​the black portion surrounded by the IR spectrum and the baseline formed by 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.

[0024] 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 and more excellent aesthetics, and also tends to be less susceptible to rusting of equipment (e.g., piping) during high-temperature treatment during recycling. From the same viewpoint, the film of this embodiment preferably has a PVDC fraction index by Raman spectroscopy of 4.0 to 14.0, more preferably 4.0 to 10.0.

[0025] 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.

[0026] In this embodiment, the peak area derived from PVDC in formula (2) is 405 to 450 cm -1 and 467-495cm -1The 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.

[0027] When the film of this embodiment is measured by thermogravimetric analysis in an air atmosphere, scanning from room temperature to 1000°C at a temperature increase rate of 10°C / min, the weight loss at 270°C is preferably 40% by weight or less, the weight loss at 260°C is preferably 35% by weight or less, and the weight loss at 250°C is preferably 30% by weight or less.

[0028] When the film of this embodiment has a weight loss at each temperature within the above range, rust tends to be less likely to form on equipment (such as piping) during high-temperature treatment during recycling.

[0029] From the same viewpoint, when the film of this embodiment is measured by thermogravimetric analysis in an air atmosphere, scanning from room temperature to 1000°C at a heating rate of 10°C / min, the weight loss at 270°C is more preferably 0.0 to 40.0 wt%, even more preferably 0.0 to 27.0 wt%, and most preferably 0.0 to 22.5 wt%, the weight loss at 260°C is more preferably 0.0 to 35.0 wt%, even more preferably 0.0 to 24.0 wt%, and most preferably 0.0 to 18.5 wt%, and the weight loss at 250°C is more preferably 0.0 to 30.0 wt%, even more preferably 0.0 to 21.0 wt%, and most preferably 0.0 to 15.0 wt%.

[0030] The method for controlling the weight loss at each temperature of the film of the present embodiment to fall within the above range is not particularly limited, but an example thereof includes a method of mixing a vinylidene chloride resin composition (PVDC) with a vinyl chloride resin composition (PVC) as a raw material for the film.

[0031] In this embodiment, the weight loss at each temperature can be measured specifically by the method described in the Examples below.

[0032] The film of this embodiment preferably has a thickness of 6 μm to 10 mm. When the thickness of the film of this embodiment is within this range, the film tends to have a relatively uniform particle size when crushed, making it easier to recycle. 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.

[0033] [Film components] The film of this embodiment 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 50 wt%, more preferably 5 to 40 wt%, and even more preferably 5 to 15 wt%. Furthermore, in the film of this embodiment, the content of the vinyl chloride resin composition (PVC) is preferably 50 to 95 wt%, more preferably 60 to 95 wt%, and even more preferably 85 to 95 wt%. When the contents of the vinylidene chloride resin composition (PVDC) and the vinyl chloride resin composition (PVC) are within the above ranges, dehydrochlorination tends to be less likely to occur, and the recycled material tends to have excellent stability during high-temperature treatment.

[0034] 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).

[0035] 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.

[0036] 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.

[0037] The vinylidene chloride resin composition contained in the film of the present embodiment may be a petroleum-derived resin or a plant-derived resin.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] The vinyl chloride resin composition contained in the film of the present embodiment may be a petroleum-derived resin or a plant-derived resin.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] The film of the present embodiment may contain a liquid component.

[0048] 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.

[0049] 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.

[0050] 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 PVDC fraction index of the film of this embodiment to be controlled within the above-mentioned range in IR.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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]

[0055] 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.

[0056] The measurement and evaluation methods used in the examples and comparative examples are as follows.

[0057] (1) 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).

[0058] (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).

[0059] (3) 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.

[0060] (4) Weight loss at each temperature The weight loss of the molded articles (films) obtained in the examples and comparative examples was measured at 250°C, 260°C, and 270°C by simultaneous thermogravimetry and differential thermal analysis (TG-DTA), which scanned from room temperature to 1000°C at a heating rate of 10°C / min in an air atmosphere (200 mL / min). The measurement device used was a NEXTA STA200RV (Hitachi High-Tech Science Corporation). Software for NEXTA was used as the analysis software.

[0061] (5) Stability of recycled materials during high-temperature treatment 5.00 g of the crushed compact was evenly distributed on an iron plate measuring 7 cm wide, 15 cm long, and 1 mm thick, and heated at 270°C for 6 seconds. After heating, the iron plate was left to stand in an atmosphere of 23±2°C and 50±10% RH for 96 hours. The degree of rust was then visually confirmed and rated on a 5-point scale of A, B, C, and D. (Evaluation criteria) A: When treated at high temperatures, the iron plate hardly rusts. B: The iron plate is less likely to rust when treated at high temperatures. C: The iron plate is relatively resistant to rust when treated at high temperatures. D: Rust occurs on steel plates when they are treated at high temperatures.

[0062] (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).

[0063] [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).

[0064] [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.

[0065] [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.

[0066] [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.

[0067] [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.

[0068] [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.

[0069] [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).

[0070] [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.

[0071] [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.

[0072] [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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] [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.

[0080] 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).

[0081] [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).

[0082] [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).

[0083] [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).

[0084] [Table 1]

[0085] [Table 2]

[0086] [Table 3]

Claims

1. A film in which a vinylidene chloride resin composition (PVDC) and a vinyl chloride resin composition (PVC) have a PVDC fraction index of 0.5 to 10.0, as expressed by the following formula (1), when 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)

2. 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)

3. 3. The film according to claim 1 or 2, wherein, when measured by thermogravimetric analysis in an air atmosphere by scanning from room temperature to 1000°C at a heating rate of 10°C / min, the film exhibits a weight loss of 40% by weight or less at 270°C, a weight loss of 35% by weight or less at 260°C, and a weight loss of 30% by weight or less at 250°C.

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

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