JP7173793B2 - Wrap film and wrap film roll - Google Patents

Description

TECHNICAL FIELD The present invention relates to a wrap film and a wrap film roll using the same.

Conventional wrap films have excellent properties such as adhesion between films and adherends, gas barrier properties against gases such as water vapor and oxygen, and cutability when used in a cosmetic box. It is used in many households as a wrap film. Household wrap films are mainly used for food storage in refrigerators and freezers, and for heating food in containers in microwave ovens.

Among the wrap films currently on the market for home use, the one that is evaluated as being the most convenient to use is a film mainly composed of a polyvinylidene chloride resin. On the other hand, films mainly composed of polyethylene-based resin, polypropylene-based resin, polyvinyl chloride-based resin, poly-4-methylpentene-1 resin, etc. are also commercially available, but all of them are polyvinylidene chloride-based. It does not match the adhesion of resin wrap film and is inferior in wrapping suitability, and vinylidene chloride wrap is widely used.

For example, Patent Literatures 1 and 2 disclose techniques related to the property of being easy to cut in the width direction in addition to the property of preventing longitudinal tearing in the machine direction of the film.

Further, Patent Document 3 discloses a technique for improving the adhesiveness and the oxygen/water vapor barrier properties when a metal or metal oxide is vapor-deposited by means of a fibril structure on the surface.

Japanese Patent No. 5501791 International Publication No. 2016/189987 Pamphlet JP-A-11-077824

Wrapping suitability of household wrap films requires not only transparency and cuttability, but also firmness and firmness. In addition, it is required to have stability with little melt perforation, large deformation, fusion to the container, or deterioration of itself during cooking in a microwave oven. be. In addition to adhesion, consumers are also strongly demanding good pull-out properties when pulling out the wound wrap film from the cosmetic box, which are contradictory properties.

However, none of Patent Documents 1 to 3 has achieved a wrap film having a sufficient unwinding suppressing effect when cut, oxygen/water barrier properties, adhesion properties, and transparency.

The present invention provides a novel wrap film with good wrapping aptitude, excellent rewinding suppression effect when cut, good oxygen and water barrier properties, good adhesiveness during use, and transparency. That's what it is.

The present inventors have made intensive studies from the viewpoint of the effect of suppressing unwinding during cutting, good oxygen and water barrier properties, and excellent adhesion and transparency. The present inventors have found that the above problems can be solved by controlling the hardness within a specific range, resulting in the present invention. That is, the present invention relates to the following.
(1)
Oxygen permeability is 110 cm ³ /m ² ·day·atm at 23°C or less, and water vapor permeability is 20 g/m ² ·
A wrap film characterized by a day at 38°C and 90% RH or less.
(2)
The wrap film according to (1) above, which has a crystal long period of 12.5 nm or less.
(3)
The surface of at least one layer has a network structure that can be observed with a phase image of an atomic force microscope, the network of the network structure is composed of fibrils, and the average width of the observed fibrils in the network structure is 145 nm or less. The wrap film according to (1) or (2) above.
(4)
The wrap film according to any one of (1) to (3) above, which has a thickness of 5 to 15 μm.
(5)
The wrap film according to any one of (1) to (4) above, which contains a copolymer consisting of 85 to 97% by mass of a vinylidene chloride monomer and 15 to 3% by mass of a vinyl chloride monomer. .
(6)
A step of stretching an unstretched sheet in both the machine direction and the direction perpendicular to the machine direction, wherein the draw ratio in the machine direction is 4.0 or less and the draw ratio in the direction perpendicular to the machine direction is 5.8 or more. The method for producing a wrap film according to any one of (1) to (5) above.
(7)
A wound body in which the wrap film according to any one of (1) to (5) above is wound around a core.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a novel wrap film having good wrapping properties, good adhesion during use, excellent oxygen and water barrier properties, transparency, and an anti-rewinding effect.

1 is a schematic diagram of a network structure observed in a phase image of an atomic force microscope (AFM); FIG. 1 is an atomic force microscope (AFM) phase image of the wrap film surface of Example 1 of the present application. 2 is an atomic force microscope (AFM) phase image of the wrap film surface of Comparative Example 1 of the present application. 1A to 1D are conceptual diagrams of an example of a method for manufacturing a wrap film according to an embodiment;

EMBODIMENT OF THE INVENTION Hereinafter, the form (henceforth "this embodiment") for implementing this invention is demonstrated in detail below. It should be noted that the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.

The wrap film of the present embodiment is characterized by having an oxygen permeability of 110 cm ³ /m ² ·day·atm at 23°C or less and a water vapor permeability of 20 g/m ² ·day at 38°C and 90% RH or less. and

[Components of wrap film]
The wrap film of the present embodiment is preferably made of constituents containing polymers.

In the present embodiment, the polymer is a polymer with film-forming ability. This polymer means a polymer that accounts for 50% by weight or more of the entire film.

As will be described later, an amorphous polymer cannot form a surface network structure effective for imparting adhesiveness, so it is preferable not to use it as the polymer that is the main component of the film in this embodiment.

However, even an amorphous polymer can be blended and used as long as the amount is enough to partially crystallize the crystalline polymer. In addition, crystalline polymers and hydrogen-bonding polymers such as cellulose and aromatic polyamides, which do not have a definite crystal melting point, may be used. Since a process such as solvent recovery is required, it is disadvantageous in terms of operation. From the viewpoint of operability, a polymer having a crystalline melting point of 350° C. or less, which can be melt-molded in the manufacturing process, is preferably used.

Polyvinylidene chloride-based resins, polyolefin-based resins, polyester-based resins, and polyamide-based resins are preferably used as polymers forming the wrap film of the present embodiment. For example, polyolefin resins include polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and copolymers mainly composed of these, and polyester resins include polyethylene terephthalate, polypropylene terephthalate, poly-1,4- Cyclohexanedimethylene terephthalate, polyethylene-2,6-naphthalate, polylactic acid, polyhydroxyglycolic acid, etc. Polyamide resins include nylon 6, nylon 7, nylon 66, nylon 610, nylon 612, nylon 46, nylon 6T and the like. can do

Polymers forming the wrap film of the present embodiment more preferably include a polyvinylidene chloride resin composition. The polyvinylidene chloride-based resin composition may be a homopolymer of a vinylidene chloride monomer, or a copolymer of a vinylidene chloride monomer and a monomer copolymerizable therewith. As used herein, a polyvinylidene chloride-based resin wrap film refers to a wrap film containing a polyvinylidene chloride-based resin composition. The polyvinylidene chloride resin composition may contain one polyvinylidene chloride resin, or may contain two or more polyvinylidene chloride resins.

The monomer copolymerizable with the vinylidene chloride monomer is not particularly limited, and examples thereof include vinyl chloride, acrylic acid esters such as methyl acrylate and butyl acrylate, and methacrylic acid esters such as methyl methacrylate and butyl methacrylate. , acrylonitrile, vinyl acetate and the like. Among these, vinyl chloride is preferable from the viewpoint of easy balance between oxygen/water barrier properties and extrusion processability and excellent film adhesion. These may be used individually by 1 type, and may use 2 or more types together.

When a copolymer of a vinylidene chloride monomer and the above monomer is used, from the viewpoint of crystallinity, workability, film properties, etc., the vinylidene chloride monomer is 85 to 97% by mass, and A copolymer containing 15 to 3% by mass of a copolymerizable monomer is preferred. By setting the vinylidene chloride monomer ratio to 85% by mass or more, it is possible to further improve oxygen/water barrier properties and film cutting properties, and by setting the vinylidene chloride monomer ratio to 97% by mass or less, workability is improved. can be further improved. The monomer ratio is a value calculated from the integration ratio of the peaks derived from each monomer component in the ¹ H-NMR spectrum measured by FX-270 (manufactured by JEOL Ltd.) using d-THF as a solvent.

The weight average molecular weight of the polyvinylidene chloride resin composition is not particularly limited, but is preferably 70,000 to 110,000, more preferably 80,000 to 100,000. By setting the weight-average molecular weight of the polyvinylidene chloride-based resin composition to the above lower limit or more, it is possible to obtain a better film strength, and by setting it to the above upper limit or less, the processability can be further improved. . Here, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) using tetrahydrofuran as a mobile phase, calibrated with polystyrene having a known molecular weight, and converted.

Additives such as known plasticizers and stabilizers can be added to the polyvinylidene chloride resin composition. The plasticizer is not particularly limited, and known ones can also be used. Examples include acetyl tributyl citrate, acetylated monoglyceride, dibutyl sebacate and the like. The stabilizer is not particularly limited, and known stabilizers can also be used. Examples include epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil.

In addition, known weather resistance improvers, antifog agents, antibacterial agents, oligomers such as polyester, MBS (methyl methacrylate, butadiene, styrene) used for food packaging materials, as long as the effects of the present embodiment are not impaired. You may add polymers, such as. The weather resistance improver is not particularly limited, and known ones can also be used. Examples thereof include UV absorbers such as 2-(2'-hydroxy-3'5'-di-tert-butylphenyl)-5-chlorobenzotriazole. The anti-fogging agent is not particularly limited, and known ones can also be used. Examples thereof include surfactants such as glycerin fatty acid ester, diglycerin fatty acid ester, and sorbitan fatty acid ester. The antibacterial agent is not particularly limited, and known agents can also be used. Examples thereof include natural antibacterial agents such as grapefruit seed extract and moso bamboo extract.

The wrap film of the present embodiment does not necessarily have a single composition of one layer, and in the case of a multilayer structure, the layer in contact with the container is mainly composed of a crystalline polymer and has a network structure observed in an AFM phase image. It may have a multi-layered structure of two or more layers without any change in practical adhesion as long as it contains a liquid component.

The wrap film of this embodiment may contain a liquid component.

The liquid component that is preferably used differs depending on the type of polymer. From the viewpoint of imparting flexibility to the film, at least one of them is preferably an aliphatic hydrocarbon polymer having an alkyl group or a methylene chain moiety in the liquid component. , Ester-based polymers, and amide-based polymers, those containing functional groups capable of hydrogen bonding, such as carbonyl groups, ether groups, and hydroxyl groups, are preferably used.

For example, those having an alkyl group include mineral oil, liquid paraffin, and saturated hydrocarbon compounds. Those containing functional groups capable of hydrogen bonding such as carbonyl groups, ether groups, and hydroxyl groups include aliphatic alcohols, alicyclic alcohols, these polyhydric alcohols, and the above-mentioned alcohol components and aliphatic or aromatic (poly carboxylic acid esters, aliphatic hydroxycarboxylic acid esters with alcohols and/or fatty acids, modified products of these esters, and polyoxyethylene alkyl ethers and/or esters thereof. More specifically, for example, polyglycerols such as glycerin, diglycerin, triglycerin, and tetraglycerin, and these are used as raw materials for alcohol components, and fatty acids such as lauric acid, palmitic acid, stearic acid, and olein are used as acid components. mono-, di-, triesters, polyesters, etc. with acids, linoleic acid, etc.; or esters of sorbitan with the above fatty acids; Esters of aliphatic hydroxycarboxylic acids such as citric acid, malic acid and tartaric acid with lower alcohols having 10 or less carbon atoms, or polyvalent carboxylic acids such as malonic acid, succinic acid, glutaric acid and adipic acid with aliphatic alcohols. Examples of esters or modified products of these esters include epoxidized soybean oil and epoxidized linseed oil. In particular, when used as a wrap for food packaging, a liquid component that is a food additive stipulated by the Food Sanitation Law is preferably used. From the viewpoint of heat resistance, liquid components having a boiling point of 200° C. or higher are preferably used.

[Surface structure of wrap film]
The wrap film of the present embodiment preferably has, on the surface of at least one layer, a network structure that can be observed with a phase image of an atomic force microscope (hereinafter also referred to as "AFM").

In the wrap film of the present embodiment, the network structure preferably has an average width of 145 nm or less of fibrils forming the network observed with an AFM phase image. When the average width of fibrils is 145 nm or less, the film strength is moderate and cuttability is improved. In addition, the occurrence rate of rewinding is reduced by improving the cuttability.

In addition, when the average width of the fibrils is 1 nm or more, the network structure is sufficient to retain the additives on the surface, the adhesion is moderate, and the extractability is improved, which is preferable. The average width of fibrils is more preferably 10 nm to 145 nm from the viewpoint of practical usability. Even more preferably 45 nm to 145 nm.

Here, the AFM phase image is an image obtained by imaging the phase information with respect to the stimulus of the AFM cantilever. In the wrap film of the present embodiment, the mesh structure is, for example, fibril portions where the phase delay with respect to the stimulation of the cantilever is small, and holes where the phase delay is large. are pores, and bright areas are fibrils. That is, when comparing fibrils and pores, the pores are more amorphous.

In this embodiment, the average width of fibrils can be measured by the method described in Examples below.

In addition, in the wrap film of the present embodiment, there are various methods for forming the network structure on the surface. For example, the network structure can be formed by oriented crystallization during the process of biaxial stretching. In the wrap film of the present embodiment, it is preferable to form the above-described network structure by carrying out biaxial stretching in order to develop the network structure. However, in the case of wet film formation, even if there is no active stretching, if there is a process such as desolvation under tension, the shrinkage stress will substantially stretch the film, so free shrinkage must occur. If so, active biaxial stretching may not be performed.

As for the timing of stretching, if the crystallization speed of the polymer is high, the polymer may be extruded from a molten state, air-cooled, and stretched while being crystallized. When the film is stretched at 100° C., crystallization does not follow, effective oriented crystallization may not occur, and a network structure may not be developed. In addition, a nucleating agent may be added as appropriate to increase the crystallization rate.

[Crystal long period of wrap film]
Further, the wrap film of the present embodiment preferably has a crystal long period of 12.5 nm or less, more preferably 8.2 nm to 12.5 nm. When the crystal length period is 8.2 nm or more, the film has sufficient strength when cut, and in the case of a winding wrap for food packaging, cuttability when cut is improved, and the wrap film is rewound. rate is also reduced. In addition, since the crystal structure developed after stretching is formed, the oxygen/water barrier properties are also improved.

On the other hand, when the crystal long period is 12.5 nm or less, the film is easily cut, and in the case of a winding wrap for food packaging, cuttability is improved and the unwinding ratio is lowered. In addition, by preventing the ratio of the amorphous region existing between the crystal long periods from becoming excessively high, the generation of voids in the interface region between the crystal and the amorphous is prevented, and the oxygen and water barrier properties are also improved. . The crystal long period is more preferably 9.0 nm to 12.5 nm from the viewpoint of practical usability.

In addition, in the present embodiment, the crystal long period can be measured by the method described in Examples below.

[Evaluation of oxygen and water barrier properties]
In general, wraps are required to have oxygen barrier properties and water barrier properties in order to maintain freshness. The wrap film of the present embodiment preferably has an oxygen permeability X (cm ³ /m ² ·day · atm at 23°C) in the range of 1≤X≤110. When the oxygen permeability is in the range of 1≦X≦110, the oxygen barrier property is sufficient and the freshness of food is sufficiently maintained. When X<1, it may be difficult to exhibit sufficient freshness-keeping performance, and when X>110, it tends to be difficult to exhibit sufficient barrier properties. It is more preferably 1≦X≦77, and more preferably 1≦X≦50 in view of practical use. Further, the wrap film of the present embodiment preferably has a water vapor permeability Y (g/m ² ·day at 38° C., 90% RH) in the range of 1≦Y≦20. When the water vapor permeability is in the range of 1≦Y≦20, the water vapor barrier property is sufficient, and the freshness of food is sufficiently maintained. When Y<1, it may be difficult to exhibit sufficient freshness-keeping performance, and when Y>20, it tends to be difficult to exhibit sufficient barrier properties. It is more preferably 1≤Y≤18, and more preferably 1≤Y≤10 from the viewpoint of practical usability.

The method for controlling the oxygen permeability and the water vapor permeability in the above range is not particularly limited, but for example, the draw ratio is set to 4.0 or less (preferably 3.8 or less) in the flow direction, in the direction perpendicular to the flow direction. : 5.8 or more, using a polymer with a low glass transition temperature, or adding a nucleating agent appropriately.

Incidentally, in the present embodiment, the oxygen permeability and the water vapor permeability can be measured by the methods described in Examples below.

[Method for producing wrap film]
Next, an example of the method for manufacturing the cling film of the present embodiment will be described. Various methods can be employed for producing a wrap film containing a polyvinylidene chloride-based resin composition, but an inflation film-forming method is usually employed. That is, according to this embodiment, the wrap film can be obtained by inflation molding. More preferably, the wrap film of the present embodiment is a polyvinylidene chloride-based resin wrap film obtained by stretching the polyvinylidene chloride-based resin composition described above at least in the MD direction, followed by inflation molding. In the inflation film forming method, for example, a polyvinylidene chloride resin composition is melt-extruded into a tubular shape from a circular die, and then the outside of the tubular resin is brought into contact with a coolant such as cold water filled in a storage tank called a cold water tank. At that time, in a state in which the refrigerant is injected into and stored in the tubular (cylindrical) resin sandwiched between the die port and the pinch roll, the inside is brought into contact with a refrigerant such as mineral oil to solidify into a film. to mold. In this specification, the tubular resin portion (extrusion) sandwiched between the die mouth and the pinch roll is referred to as a "sock". The coolant (liquid) injected into the sock is called "sock liquid". The sock is folded by the pinch rolls or the like to form a tubular double-ply film, which is called a "parison".

The inflation film forming method will be described in more detail below. FIG. 4 is a conceptual diagram of an example of the method of manufacturing the wrap film of the present embodiment.

First, in the extrusion process, the molten polyvinylidene chloride resin composition is extruded into a tubular shape from the die port (3) of the circular die (2) by the extruder (1), and the sock (tubular polyvinylidene chloride resin composition Entity) (4) is formed.

Next, in the cooling and solidification step, the outside of the extruded sock (4) is brought into contact with cold water in a cold water tank (6), and the sock liquid (5) is injected into the inside of the sock (4) by a conventional method. The sock (4) is cooled and solidified from the inside and outside by storing it in the water. At this time, the inside of the sock (4) is coated with the sock liquid (5). The solidified sock (4) is folded by a first pinch roll (7) to form a double-ply sheet parison (8). The amount of sock liquid applied is controlled by the pinch pressure of the first pinch roll (7).

As the sock liquid, water, mineral oil, alcohols, polyhydric alcohols such as propylene glycol and glycerin, cellulose-based and polyvinyl alcohol-based aqueous solutions, and the like can be used. These may be used singly or in combination of two or more. Further, the sock liquid may be added with the above-described weather resistance improver, anti-fogging agent, antibacterial agent, etc., which are used in food packaging materials, as long as they do not impair the effects of the present embodiment.

The coating amount of the sock liquid is not particularly limited, but is preferably 50 to 20,000 ppm, more preferably 100 to 15,000 ppm, and still more preferably 150 to 10,000 ppm from the viewpoint of parison openness and film adhesion. Here, the coating amount (ppm) is the mass of the sock liquid applied to the sock expressed in ppm by mass with respect to the total mass of the sock.

Subsequently, by injecting air into the inside of the parison (8), the parison (8) is opened again and becomes tubular. The parison (8) is reheated with hot water (not shown) to a temperature suitable for stretching. Hot water adhering to the outside of the parison (8) is squeezed out by the second pinch roll (9). Next, in the inflation process, air is injected into the tubular parison (8) heated to an appropriate temperature to form bubbles (10) by inflation stretching, thereby obtaining a stretched film.

The crystal long period of the wrap film can be controlled by the draw ratio and the crystallinity of the polymers that make up the wrap film. The crystal long period tends to increase as the draw ratio in the TD direction increases compared to the draw ratio in the MD direction, and the crystal long period tends to increase as the crystallinity of the polymer increases. .

The method for producing a wrap film of the present embodiment preferably includes a step of stretching the unstretched sheet in the machine direction and the direction perpendicular to the machine direction. In this case, the draw ratio in the TD direction is 5.8 times or more. And, the draw ratio in the MD direction is preferably 4.0 times or less, and from the viewpoint of film-forming properties, the draw ratio in the MD direction is more preferably 3.4 times or more and 3.8 times or less. Although the upper limit of the draw ratio in the TD direction is not particularly limited, it is, for example, 8.5 times or less.

A method for controlling the draw ratio is not particularly limited, and a known method can be adopted. For example, there is a method of controlling the stretching temperature by changing the temperature of hot water for reheating. In order to lower the draw ratio, the lower the draw temperature, the more stable the inflation bubbles at a low draw ratio, which is preferable. At that time, the stretching temperature is preferably higher than the stretching room temperature from the viewpoint of the stability of inflation bubbles. The stretching temperature is more preferably 34°C or less, still more preferably 25°C to 34°C. As the stretching temperature, the temperature is measured at an intermediate point in the MD direction between the point at which stretching in the MD and TD directions is completed and the point at which winding is started.

The stretched film is then folded by a third pinch roll (11) to form a double-ply film (12). The double-ply film (12) is wound on a winding roll (13). Further, the film is slit and peeled into one film (single peel). Finally, this film is wound around a core such as a paper tube to obtain a wrap film roll wrapped around a paper tube.

The crystal length period is affected not only by the draw ratio but also by the heat history. When the wrap film is subjected to heat history, the crystal long period tends to decrease and the tear strength tends to decrease. Therefore, it is preferable not to subject the wrap film to excessive heat history. For example, not only when aging treatment is performed, but also in various environments such as when transporting the wrap film in the summer or when the wrap film is placed near a heat source such as a stove when used at home. It is preferable to avoid thermal history, which can prevent the crystal long period from becoming too low and the film from being prone to tearing.

The above description is an example of the method of manufacturing the cling film of the present embodiment, and may be performed using various apparatus configurations and conditions other than those described above. For example, other known methods may be employed.

[Wound body]
The wrap film of the present embodiment can be used in various forms, for example, it can be a roll-shaped polyvinylidene chloride-based resin wrap film. When a roll-shaped wrap film is used, it may or may not have a core.

When it is wound around a core, for example, it is a wrap film roll comprising a cylindrical core and the polyvinylidene chloride resin wrap film of the present embodiment wound around the core. be able to. A wound body means a body in the form of a roll obtained by winding a wrap film around a core or the like.

The wrap film of the present embodiment can effectively suppress unwinding troubles that occur when using a roll-shaped wrap film or the like. The material, size, etc. of the core are not particularly limited, and a known core such as a paper tube can be used. Furthermore, if the wrap film is roll-shaped, it may or may not have a core. The wrap film roll of the present embodiment can be used by being stored in a decorative box having a cutting blade for cutting the wrap film.

[Thickness of wrap film]
Although the thickness of the wrap film of the present embodiment is not particularly limited, it is preferably 5 to 30 μm, more preferably 5 to 15 μm, from the viewpoints of usability and optical properties.

[Evaluation of adhesion]
Next, it is preferable that the wrap film of the present embodiment has an adhesion work amount X (mJ/25 cm ² ) in the range of 1≦X≦2.5. When 1≦X, the wrap film tends to exhibit sufficient adhesiveness. Further, when X≦2.5, the wrap film can be easily peeled off, and so-called excessive adhesion can be suppressed. From the point of view of practical use, 1.5≦X≦2.4 is more preferable, and 1.8≦X≦2.3 is even more preferable.

In the present embodiment, the amount of adhesion work can be measured by the method described in Examples below.

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples. In addition, the following measurement methods were used for observation of the surface network structure of the wrap film by AFM, evaluation of the crystal long period of the wrap film, tear strength of the wrap film, unwinding ratio, adhesion and transparency.

(1) AFM measurement A film was adhered and fixed to a Si wafer, and a phase image of the surface was observed in tapping mode with a Dimension Icon manufactured by Bruker. A Si single crystal cantilever (spring constant catalog value 40 N/m) was used for the measurement, and the scan rate was 0.5 to 2 Hz, the scan size was 1 μm × 1 μm, and the number of sampling points was 512 × 256 or 512 × 512. . The contact pressure of the cantilever was controlled by the film. When the target amplitude was 400 mV, the set point was 240-320 mV, and when the target amplitude was 800 mV, the set point was 450-500 mV. When measuring the fibril width (fibril diameter), one image is divided into four for each phase image, and five fibrils that are considered typical are selected for each region. was taken as the average fibril width.

(2) Crystal long period measurement The crystal long period was determined by small-angle X-ray scattering (SAXS) measurement under the following equipment and conditions.
Device NANOPIX manufactured by Rigaku Corporation
X-ray incidence direction Film normal direction X-ray wavelength 0.154 nm
Optical system Point collimation
(1st: 0.55mmΦ, 2nd: Open, guard: 0.35mmΦ)
Detector HyPix-6000 (two-dimensional detector)
Camera length SAXS: 1113mm
Exposure time Comparative Examples 5 to 8, 10, 12: 10 minutes/1 sample
Examples 1 to 9, Comparative Examples 1 to 4, 9, 11: Detector background correction and empty cell scattering correction were performed on the X-ray scattering patterns obtained from 1 hour/1 sample HyPix-6000. A ring average was then performed to obtain the SAXS profile I(q). Furthermore, the SAXS profile ^I (q) was subjected to Lorentz correction by multiplying by q2. The Bragg angle θ is calculated from the magnitude of the scattering vector of the peak derived from the crystal long period of the Lorentz-corrected SAXS profile (equation 1), and this is substituted into the Bragg equation (equation 2), and the crystal long period d is Calculated.

q=4π sin θ/λ Formula (1)
θ: Bragg angle q: Magnitude of scattering vector λ: X-ray wavelength

2d sin θ=λ Formula (2)
d: crystal long period θ: Bragg angle λ: X-ray wavelength

(3) Tear strength Measured according to ASTM-D-1992. The measurement was performed in an atmosphere of 23° C. and 50% RH. Using a light load tear tester (manufactured by Toyo Seiki Co., Ltd.), the tear strength in the MD and TD directions was measured (unit: cN).

(4) Rewind rate A cut test was performed using a commercially available plastic wrap film box (Saran Wrap (registered trademark) cosmetic box manufactured by Asahi Kasei Home Products Co., Ltd., 30 cm x 20 m). The test was conducted in an atmosphere of 23° C. and 50% RH. The film was cut with the opening of the cosmetic box fixed at 30°, and the probability (%) of occurrence of rewinding of the film when pulling out the cut film was calculated. The number of N was 500 (unit: %).

(5) Oxygen Permeability Using OX TRAN 2/21MH (trade name) manufactured by MOCON, the oxygen permeability was measured according to ASTM D3985. The value 4 hours after setting the sample in the device was adopted. The measurement was performed at 23°C. The smaller the oxygen permeability, the higher the oxygen barrier properties.

(6) Water Vapor Permeability A PERMATRAN W-398 (trade name) manufactured by MOCON was used to measure the water vapor permeability according to ASTM F1249. The value 3 hours after setting the sample in the device was adopted. Measurement was performed under conditions of 38° C. and 90% RH. The lower the water vapor permeability, the higher the water barrier properties.

(7) Adhesion Assuming that wrap films are used at home, the adhesion between wrap films was evaluated. The measurement was performed in an atmosphere of 23° C. and 50% RH. First, two aluminum jigs having a bottom area of 25 cm ² , a height of 55 mm and a weight of 400 g were prepared, and filter paper having the same area as the bottom area was attached to the bottom surface of both jigs. The bottoms of both jigs to which the filter papers were pasted were covered with a wrap film to prevent wrinkles, and were held down with a rubber band and fixed. The two jigs were put together so that the bottom faces on the side covered with the wrap film overlapped with each other, and they were crimped for 1 minute with a load of 500 g. Then, the work required when both wrap film surfaces were peeled off perpendicularly to each other at a speed of 5 mm/min using a tensile compression tester (manufactured by Shimadzu Corporation) was measured (unit: mJ/25 cm ² ). ).

(8) Haze Measured according to JIS-K-7136. The measurement was performed in an atmosphere of 23° C. and 50% RH. Haze was measured using a turbidity meter (manufactured by Nippon Denshoku Co., Ltd.) (unit: %).

[Example 1]
A polyvinylidene chloride resin composition of vinylidene chloride (VDC)/vinyl chloride (VC) = 88/12 (mass ratio) having a weight average molecular weight of 90,000 is melted at a temperature of 170°C and melted with a melt extruder. The parison obtained by extrusion was inflation-stretched into a tubular film. The weight average molecular weight is a value measured by gel permeation chromatography (GPC) using tetrahydrofuran as a mobile phase, calibrated with polystyrene having a known molecular weight, and converted.
At this time, the draw ratio in the MD direction was set to 3.7 times, and the draw ratio in the TD direction was set to 5.8 times. Also, the stretching temperature was set to 25°C. After folding and winding this cylindrical film, it was slit to a width of 300 mm, peeled off so as to form one film, and wound 20 m on a paper tube with an outer diameter of 36.6 mm and a length of 305 mm, and a thickness of about 10 μm. A wrap film wrapped around a paper tube was produced.
Table 1 shows the evaluation results of AFM measurement, SAXS measurement, tear strength, unwinding rate, oxygen permeability, water vapor permeability, adhesion and transparency of the obtained film.

[Example 2]
A polyvinylidene chloride resin composition of vinylidene chloride (VDC)/vinyl chloride (VC) = 88/12 (mass ratio) is melted at a temperature of 170°C and melt-extruded with a melt extruder to obtain a parison, It was inflation-stretched to form a tubular film.
The draw ratio in the MD direction was set to 3.6 times, and the draw ratio in the TD direction was set to 6.1 times. The stretching temperature was set at 34°C. Other than that, the operation according to Example 1 was performed to produce a paper tube-wound wrap film having a thickness of about 10 μm.
Table 1 shows the evaluation results of the obtained film.

[Example 3]
A polyvinylidene chloride resin composition of vinylidene chloride (VDC)/vinyl chloride (VC) = 88/12 (mass ratio) is melted at a temperature of 170°C and melt-extruded with a melt extruder to obtain a parison, It was inflation-stretched to form a tubular film.
The draw ratio in the MD direction was set to 3.5 times, and the draw ratio in the TD direction was set to 6.2 times. The stretching temperature was set at 31°C. Other than that, the operation according to Example 1 was performed to produce a paper tube-wound wrap film having a thickness of about 10 μm.
Table 1 shows the evaluation results of the obtained film.

[Example 4]
A parison obtained by mixing and melting a liquid component (15 parts by weight of glycerin diacetate monolaurate) with a crystalline polymer (85 parts by weight of polylactic acid), which is the main component, at a temperature of 220° C., followed by melt extrusion with a melt extruder. was inflation-stretched to form a tubular film.
The draw ratio in the MD direction was set to 3.6 times, and the draw ratio in the TD direction was set to 5.9 times. The stretching temperature was set at 26°C. Other than that, the operation according to Example 1 was performed to produce a paper tube-wound wrap film having a thickness of about 10 μm.
Table 1 shows the evaluation results of the obtained film.

[Example 5]
A polyvinylidene chloride resin composition of vinylidene chloride (VDC)/vinyl chloride (VC) = 88/12 (mass ratio) is melted at a temperature of 170°C and melt-extruded with a melt extruder to obtain a parison, It was inflation-stretched to form a tubular film.
The draw ratio in the MD direction was set to 3.4 times, and the draw ratio in the TD direction was set to 5.8 times. The stretching temperature was set at 25°C. Other than that, the operation according to Example 1 was performed to produce a paper tube-wound wrap film having a thickness of about 10 μm.
Table 1 shows the evaluation results of the obtained film.

[Example 6]
A polyvinylidene chloride resin composition of vinylidene chloride (VDC)/vinyl chloride (VC) = 88/12 (mass ratio) is melted at a temperature of 170°C and melt-extruded with a melt extruder to obtain a parison, It was inflation-stretched to form a tubular film.
The draw ratio in the MD direction was set to 3.5 times, and the draw ratio in the TD direction was set to 5.8 times. The stretching temperature was set at 25°C. Other than that, the operation according to Example 1 was performed to produce a paper tube-wound wrap film having a thickness of about 10 μm.
Table 1 shows the evaluation results of the obtained film.

[Example 7]
A polyvinylidene chloride resin composition of vinylidene chloride (VDC)/vinyl chloride (VC) = 88/12 (mass ratio) is melted at a temperature of 170°C and melt-extruded with a melt extruder to obtain a parison, It was inflation-stretched to form a tubular film.
The draw ratio in the MD direction was set to 3.8 times, and the draw ratio in the TD direction was set to 7.6 times. The stretching temperature was set at 33°C. Other than that, the operation according to Example 1 was performed to produce a paper tube-wound wrap film having a thickness of about 10 μm.
Table 1 shows the evaluation results of the obtained film.

[Example 8]
Liquid component (15 parts by weight of glycerin triacetate) and other additives (3 parts by weight of epoxidized linseed oil, 2 parts by weight of mineral oil) are mixed with the main crystalline polymer (80 parts by weight of nylon 66) at a temperature of 280°C. The resulting parison was melted and melt-extruded by a melt extruder, and inflation-stretched to form a cylindrical film.
The draw ratio in the MD direction was set to 3.7 times, and the draw ratio in the TD direction was set to 8.1 times. The stretching temperature was set at 34°C. Other than that, the operation according to Example 1 was performed to produce a paper tube-wound wrap film having a thickness of about 10 μm.
Table 1 shows the evaluation results of the obtained film.

[Example 9]
200 parts of liquid component (10 parts by weight of mineral oil) and other additives (5 parts by weight of Marukaretsu (registered trademark) ○R, 5 parts by weight of Tuftec (registered trademark) ○R) to crystalline polymer (80 parts by weight of polypropylene), which is the main component The parison obtained by mixing and melting at a temperature of 0° C. and melt extruding with a melt extruder was inflation-stretched to form a cylindrical film.
The draw ratio in the MD direction was set to 3.6 times, and the draw ratio in the TD direction was set to 6.8 times. The stretching temperature was set at 29°C. Other than that, the operation according to Example 1 was performed to produce a paper tube-wound wrap film having a thickness of about 10 μm.
Table 1 shows the evaluation results of the obtained film.

[Comparative Example 1]
A polyvinylidene chloride resin composition of vinylidene chloride (VDC)/vinyl chloride (VC) = 91/9 (mass ratio) is melted at a temperature of 170°C and melt-extruded with a melt extruder to obtain a parison, It was inflation-stretched to form a tubular film.
The draw ratio in the MD direction was set to 3.7 times, and the draw ratio in the TD direction was set to 4.3 times. Other than that, the operation according to Example 1 was performed to produce a paper tube-wound wrap film having a thickness of about 10 μm.
Table 2 shows the evaluation results of the obtained film.

[Comparative Example 2]
A polyvinylidene chloride resin composition of vinylidene chloride (VDC)/vinyl chloride (VC) = 88/12 (mass ratio) is melted at a temperature of 170°C, melt extruded with a melt extruder, and the obtained parison is , and inflation stretching to form a tubular film. The draw ratio in the MD direction was set to 5.0 times, and the draw ratio in the TD direction was set to 6.0 times. Other than that, the operation according to Example 1 was performed to produce a paper tube-wound wrap film having a thickness of about 10 μm.
Table 2 shows the evaluation results of the obtained film.

[Comparative Example 3]
Polyethylene was melted at a temperature of 170° C. and melt extruded with a melt extruder, and the obtained parison was inflation-stretched to form a cylindrical film. The draw ratio in the MD direction was set to 5.0 times, and the draw ratio in the TD direction was set to 5.0 times. Other than that, the operation according to Example 1 was performed to produce a paper tube-wound wrap film having a thickness of about 10 μm.
Table 2 shows the evaluation results of the obtained film.

[Comparative Example 4]
200 parts of liquid component (10 parts by weight of mineral oil) and other additives (5 parts by weight of Marukaretsu (registered trademark) ○R, 5 parts by weight of Tuftec (registered trademark) ○R) to crystalline polymer (80 parts by weight of polypropylene), which is the main component C., extruded from an extruder equipped with a T-die having a slit width of 20 mm.times.0.5 mm, and quenched with water to form a film sheet.
Then, while passing this raw fabric through a heating zone set at 140° C., it was successively biaxially stretched by a stretcher to 2.0×2.0 times and wound up. Other than that, the operation according to Example 1 was performed to produce a paper tube-wound wrap film having a thickness of about 10 μm.
Table 2 shows the evaluation results of the obtained film.

[Comparative Example 5]
A vinylidene chloride (VDC)/vinyl chloride (VC) = 88/12 (mass ratio) polyvinylidene chloride resin composition was mixed and melted at a temperature of 170°C, and an extruder equipped with a T die with a slit width of 20 mm × 0.5 mm. It was extruded and quenched with water to form a sheet on film.
Then, while passing this raw fabric through a heating zone set at 140° C., it was successively biaxially stretched by a stretcher to 1.0×8.6 times and wound up. Other than that, the operation according to Example 1 was performed to produce a paper tube-wound wrap film having a thickness of about 10 μm.
Table 2 shows the evaluation results of the obtained film.

[Comparative Example 6]
A vinylidene chloride (VDC)/vinyl chloride (VC) = 88/12 (mass ratio) polyvinylidene chloride resin composition was mixed and melted at a temperature of 170°C, and an extruder equipped with a T die with a slit width of 20 mm × 0.5 mm. It was extruded and quenched with water to form a sheet on film.
Then, while passing this raw fabric through a heating zone set at 38° C., it was successively biaxially stretched by a stretcher to 4.3×1.0 times and wound up. Other than that, the operation according to Example 1 was performed to produce a paper tube-wound wrap film having a thickness of about 10 μm.
Table 2 shows the evaluation results of the obtained film.

[Comparative Example 7]
A vinylidene chloride (VDC)/vinyl chloride (VC) = 88/12 (mass ratio) polyvinylidene chloride resin composition was mixed and melted at a temperature of 170°C, and an extruder equipped with a T die with a slit width of 20 mm × 0.5 mm. It was extruded and quenched with water to form a sheet on film.
Then, while passing this raw fabric through a heating zone set at 39° C., it was successively biaxially stretched by a stretcher to 5.3×1.0 times and wound up. Other than that, the operation according to Example 1 was performed to produce a paper tube-wound wrap film having a thickness of about 10 μm.
Table 2 shows the evaluation results of the obtained film.

[Comparative Example 8]
A vinylidene chloride (VDC)/vinyl chloride (VC) = 88/12 (mass ratio) polyvinylidene chloride resin composition was mixed and melted at a temperature of 170°C, and an extruder equipped with a T die with a slit width of 20 mm × 0.5 mm. It was extruded and quenched with water to form a sheet on film.
Then, while passing this raw fabric through a heating zone set at 40° C., it was successively biaxially stretched by a stretcher to 6.3×1.0 times and wound up. Other than that, the operation according to Example 1 was performed to produce a paper tube-wound wrap film having a thickness of about 10 μm.
Table 2 shows the evaluation results of the obtained film.

[Comparative Example 9]
A vinylidene chloride (VDC)/vinyl chloride (VC) = 88/12 (mass ratio) polyvinylidene chloride resin composition was mixed and melted at a temperature of 170°C, and an extruder equipped with a T die with a slit width of 20 mm × 0.5 mm. It was extruded and quenched with water to form a sheet on film.
Then, while passing this raw fabric through a heating zone set at 42° C., it was successively biaxially stretched by a stretcher to 8.0×1.0 times and wound up. Other than that, the operation according to Example 1 was performed to produce a paper tube-wound wrap film having a thickness of about 10 μm.
Table 2 shows the evaluation results of the obtained film.

[Comparative Example 10]
A vinylidene chloride (VDC)/vinyl chloride (VC) = 88/12 (mass ratio) polyvinylidene chloride resin composition was mixed and melted at a temperature of 170°C, and an extruder equipped with a T die with a slit width of 20 mm × 0.5 mm. It was extruded and quenched with water to form a sheet on film.
Then, while passing this raw fabric through a heating zone set at 49° C., it was successively biaxially stretched by a stretcher to 3.5×10.0 times and wound up. Other than that, the operation according to Example 1 was performed to produce a paper tube-wound wrap film having a thickness of about 10 μm.
Table 2 shows the evaluation results of the obtained film.

[Comparative Example 11]
A vinylidene chloride (VDC)/vinyl chloride (VC) = 88/12 (mass ratio) polyvinylidene chloride resin composition was mixed and melted at a temperature of 170°C, and an extruder equipped with a T die with a slit width of 20 mm × 0.5 mm. It was extruded and quenched with water to form a sheet on film.
Then, while passing this raw fabric through a heating zone set at 49° C., it was successively biaxially stretched by a stretcher to 5.0×7.0 times and wound up. Other than that, the operation according to Example 1 was performed to produce a paper tube-wound wrap film having a thickness of about 10 μm.
Table 2 shows the evaluation results of the obtained film.

[Comparative Example 12]
A vinylidene chloride (VDC)/vinyl chloride (VC) = 88/12 (mass ratio) polyvinylidene chloride resin composition was mixed and melted at a temperature of 170°C, and an extruder equipped with a T die with a slit width of 20 mm × 0.5 mm. It was extruded and quenched with water to form a sheet on film.
Then, while passing this raw fabric through a heating zone set at 53° C., it was successively biaxially stretched by a stretcher to 5.0×10.0 times and wound up. Other than that, the operation according to Example 1 was performed to produce a paper tube-wound wrap film having a thickness of about 10 μm.
Table 2 shows the evaluation results of the obtained film.

FIG. 2 shows an AFM phase image of the film surface obtained in Example 1. A uniform network structure was observed. A network structure was also observed in Examples 2, 3, 4, 5, 6, 7, 8 and 9 and Comparative Examples 4, 9, 10, 11 and 12. In the examples, the oxygen permeability and the water vapor permeability were within specific ranges, so the desired effects were obtained as shown in the evaluation in Table 1. However, in Comparative Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12, the oxygen permeability and the water vapor permeability are not in a specific range, so the evaluation in Table 2 As shown, the desired effect was not obtained. An AFM phase image of the film surface of Comparative Example 1 is shown in FIG.

The wrap film according to the present invention is a transparent wrap film that has an effect of suppressing unwinding when cut, has good oxygen and water barrier properties, has good adhesion during use, and is suitable for food packaging. It can be suitably used as various wrap films for packaging.

REFERENCE SIGNS LIST 1 extruder 2 circular die 3 die mouth 4 tubular vinylidene chloride resin composition (sock)
5 sock liquid 6 cold water tank 7 first pinch roll 8 parison 9 second pinch roll 10 bubble 11 third pinch roll 12 double ply film 13 take-up roll 14 holes 15 fibrils

Claims (6)

an oxygen permeability of 110 cm ³ /m ² ·day·atm at 23°C or less, and a water vapor permeability of 20 g/m ² ·day at 38°C, 90% RH or less ;
The surface of at least one layer has a network structure observed in a phase image of an atomic force microscope, the network of the network structure is composed of fibrils, and the average width of the observed fibrils in the network structure is 1 nm or more and 145 nm. and
The draw ratio in the machine direction is 3.4 to 4.0 times, and the draw ratio in the direction perpendicular to the machine direction is 5.8 to 8.5 times,
A wrap film comprising a polyvinylidene chloride resin composition . The wrap film according to claim 1, having a crystal long period of 12.5 nm or less. 3. The wrap film according to claim 1, wherein the thickness of the film is 5-15 μm. The wrap film according to any one of claims 1 to 3 , comprising a copolymer comprising 85 to 97% by mass of vinylidene chloride monomer and 15 to 3% by mass of vinyl chloride monomer. A step of stretching an unstretched sheet in both the machine direction and the direction perpendicular to the machine direction, wherein the draw ratio in the machine direction is 4.0 or less and the draw ratio in the direction perpendicular to the machine direction is 5.8 or more. The method for producing a wrap film according to any one of claims 1 to 4 , wherein A wound body in which the wrap film according to any one of claims 1 to 4 is wound around a winding core.

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