WO2011071025A1

WO2011071025A1 - Container and process for producing container

Info

Publication number: WO2011071025A1
Application number: PCT/JP2010/071850
Authority: WO
Inventors: 清一渡辺; 徹小倉; 伸輔高橋
Original assignee: 富士フイルム株式会社
Priority date: 2009-12-07
Filing date: 2010-12-06
Publication date: 2011-06-16

Abstract

Disclosed is a container obtained by winding a container with a crystalline polymer film which comprises a polymer having crystallinity and has elongated voids inside that are in such a state that the lengthwise directions of the voids have been oriented in a first direction, wherein in a cross-section of the crystalline polymer film which is orthogonal to the orientation direction of the voids, ten voids which are the shortest in the distance from the center of the void to the surface of the crystalline polymer film satisfy the following relationship (1): h(avg) > T/100 (1) where h(avg) is the arithmetic mean value of calculated distances h(i) from the respective centers to the surface of the crystalline polymer film.

Description

Container and method for manufacturing container

The present invention relates to a container in which a crystalline polymer film containing a cavity is wound around a side surface of the container, and a method for manufacturing the container.

Conventionally, from various forms to fill and package milk, milk drinks, beer, vitamin drinks, juice, carbonated drinks, water such as water and tea, or oil, seasonings and other various liquid foods Plastic bottles, glass bottles, metal cans (hereinafter referred to as “containers”) have been developed. Films describing product information and the like are wound around the surfaces of these containers.

As a method of winding such a film around a container, for example, an in-mold label blow molding method in which a bottle is formed by blowing gas into a parison with a label placed in a mold (see, for example, Patent Document 1). ) Etc. have been proposed. According to this method, it is possible to prevent the label from wrinkling or floating in a shorter cooling time without adding complicated processing to the mold or limiting the label material.

Moreover, on the surface of the container, for the purpose of protecting the container, imparting design properties, binding, labeling, etc., a part or all of the mouth, shoulder, trunk, etc. of the container is quickly covered or bound. As a packaging material to be used, a contracted film (hereinafter sometimes referred to as “shrink film”) is known.

As a packaging method using a shrink film, for example, there is a method in which a tubular or bag-like film is primarily packaged with a slight margin, and then the film is contracted (shrinked) to the outer peripheral surface of the container by hot air, steam, or the like. Are known. In addition, the film is wrapped in a certain degree of tension, the end of the film is folded into the bottom of the container, and the folded portion is primarily packaged by self-adhesion between the films or by heat-sealing, and is then subjected to a shrink treatment to prevent the film from loosening. A method such as stretch shrink for removing wrinkles is known.

Shrink wrapping can fit any shape of container, such as square, round, gourd, etc., so the container shape can be selected widely. In addition, since the shrink film and the container are not directly bonded to each other, they can be completely separated from the container. For this reason, from the viewpoint of recycling, the demand for shrinkable film that can be separated from containers is expected to increase. As shrink wrapping, a colorless shrink film or printed shrink film to add a function to display the product name, manufacturer name, contents, and design on the entire surface of these containers and the sealed part. Containers are also packaged.

Moreover, in order to protect the contents which need light-shielding properties, such as beer, cosmetics, health food, a supplement, and a pharmaceutical, from external light, it is a shrink film which added the light-shielding function by using a colored shrink film. The entire container is also packaged.
As a technique for imparting light shielding properties to the shrink film, for example, a thin film layer of metal (such as aluminum) is laminated on the shrink film (see Patent Document 2), and a white ink layer containing an aluminum paste is laminated on the shrink film. (Refer to Patent Document 3), and a light-shielding pressure-sensitive adhesive containing titanium oxide is further laminated on a shrink film containing an ultraviolet absorber (refer to Patent Document 4). These techniques provide light shielding properties by laminating a light shielding material layer on the shrink film, and the shrink film itself does not have light shielding properties. Furthermore, it is a laminate having a layer containing pigments, dyes, metals, inorganic particles and the like, and has a problem that recycling is difficult because it is not a simple structure.

In addition, the present shrink film has not been provided with a heat insulation necessary for improving the storage stability of the contents of the container.

Furthermore, recently, environmental problems such as ozone layer destruction or global warming have become a social issue and are being highlighted. Under such circumstances, it is extremely important from the viewpoint of responding to consumer needs whether environmental issues are taken into consideration for products produced by companies. For this reason, plastic beverage containers represented by PET bottles are not disposable, and effective use of resources by recycling is being promoted.
In this way, if the product is reborn as a product by recycling, the resources that are discarded can be used effectively, but for example, the process of manufacturing a PET bottle, or recycling it, requires a lot of energy even in the process of manufacturing PET bottles. The search for the direction of “providing environmentally friendly products” is also underway to reduce carbon dioxide emissions by using as little energy as possible in the process. One method is to reduce the amount of PET bottles (to reduce the amount of resin used).
For example, in the case of a PET bottle, usually about 20 g of PET resin is used in a 500 mL container. If this amount can be reduced, even if the same 500 mL PET bottled beverage is manufactured, the energy required for processing the resin can be reduced, so that resources and energy can be saved. It is thought that energy can be saved even during recycling, and carbon dioxide emissions can be reduced.

Also, when recycling containers such as PET bottles, they are crushed and transported to the factory. At that time, if the container is hard, it will not be crushed so much that it will require more energy, or if it cannot be crushed sufficiently, it will have to be transported while being bulky, and not only will it be wasted energy, but also the efficiency of conveyance will be reduced. Cost up. Therefore, in order to facilitate crushing the container, it is required to reduce the amount of resin used.

However, simply reducing the amount of resin used has the problem of reducing the strength of the container.

For example, in a cup-shaped container having an open top, there is a problem that the container is easily bent and it is difficult to reduce the thickness of the container.
In the case of a resin container having an open upper part, for example, a cup-shaped container, when the container is lifted, the holding method shown in FIG. 1 is often used. At this time, since the force is relatively concentrated on the thumb portion, if this portion is soft, the container cannot be held. Furthermore, when trying to drink beverages or the like contained inside from this state, it is necessary to tilt the container. In this case, a force to bend the container around the point where the container is supported is applied, so the force is applied particularly to the thumb part. Concentrate. If the container is fragile, when a force is applied to the finger, the container easily deforms and the beverage inside spills out, or when the finger is loosened to suppress the deformation of the container There is a concern of dropping.
For products that cannot be held well unless great care is taken to hold the container, there are very problems in use, especially for children, children, elderly people, etc. whose finger force control is not easy It is desirable that the container can be held normally without paying special attention to having the container.
Usually, the open part of the cup-shaped container is sealed by heat sealing, fitted with a lid, and also provided with a rim around the opening to improve the mouth feel when touching the mouth and to prevent the beverage from spilling. In many cases, the strength of the opening is increased.
However, with regard to the container body, it is difficult to give a special shape from the viewpoint of ease of molding, cost reduction, ease of label winding, etc., and if a special shape is given, the amount of resin used will increase significantly. As a result, there is a problem that it is no longer eco-friendly (it is difficult to appeal for eco-friendly), which is one of the factors that make it difficult to promote thinning.

For example, in the case of a PET bottle container, the holding method shown in FIG. 2 is often used when the container is held. At this time, since the force is relatively concentrated on the thumb portion, if the portion cannot withstand the applied force and is so soft that the shape cannot be maintained, the container cannot be held. In addition, when trying to drink a beverage or the like contained inside from this state, it is necessary to tilt the container, and in this case, a force is applied to bend the container around the point supporting the container. The force concentrates on the arrow 3 (see FIG. 3). If the container is fragile, there is a concern that the container may be easily deformed to spill the beverage or the like, or the container cannot be held.
Usually, the open part of the container is sealed by heat sealing, the lid is fitted, and in order to improve the mouth feel when attached to the mouth and to prevent the beverage from spilling, a rim is provided around the opening to provide an opening. The strength is improved.
However. As for the container body portion, it is difficult to give a special shape from the viewpoints of ease of molding processing, cost reduction, label winding ease, and the like, which is one of the factors that make it difficult to promote thinning.

Therefore, it is possible to quickly provide a container excellent in strength, light-shielding property, and heat retaining property, and easily compressed to reduce the volume (referred to as volume reduction), and excellent in recyclability, and a method for producing the container. The current situation is strongly demanded.

JP-A-10-128837 Japanese Patent Laid-Open No. 2003-200965 Japanese Patent Laid-Open No. 2003-200966 JP 2007-83518 A

This invention makes it a subject to solve the said conventional problems and to achieve the following objectives. That is, an object of the present invention is to provide a container that is excellent in strength, light-shielding property, and heat retention, can be easily compressed to reduce the volume, and is excellent in recyclability, and a method for producing the container. To do.

In order to solve the above-mentioned problems, the present inventors have made extensive studies and obtained the following knowledge. That is, when a polymer molded body (polymer film) made of a polymer having crystallinity such as PBT (polybutylene terephthalate), PHT (polyhexamethylene terephthalate), PBS (polybutylene succinate) or the like is stretched at a speed of 2 to 10 times, It becomes a void-containing film, and because of the hollow structure inside the film, it is considered that the film has heat retention, and the crystallization is promoted by stretching, but the container is formed by winding the film. The knowledge that the intensity can be increased, and further the knowledge that it has a high light reflection characteristic (light shielding property) over a wide wavelength range, which is considered to be caused by multiple reflection of light, in order to express a multilayer void structure, Since the film itself is produced by stretching, it has excellent shrinkage, For internal cavity structure, winding the film, a finding that it is possible to increase the strength of the container obtained by shrink.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> A container formed by winding a crystalline polymer film, which is made of a polymer having crystallinity and contains an elongated cavity inside with the length direction oriented in the first direction. And
In the cross section perpendicular to the orientation direction of the cavities in the crystalline polymer film, the ten cavities having the shortest distance from the center of the cavities to the surface of the crystalline polymer film are the crystal from each center. The distance h (i) to the surface of the conductive polymer film is calculated, and the arithmetic average value h (avg) of each calculated distance h (i) satisfies the relationship of the following formula (1): Container.
h (avg)> T / 100 (1)
However, in said Formula (1), T represents the arithmetic mean value of the thickness in the said cross section, and the ten said cavities are parallel to the arbitrary 1 straight line parallel to the said thickness direction, and the said 1 straight line. And a cavity existing in a region sandwiched by other straight lines located 20 × T apart.
<2> The container according to <1>, wherein a radius of curvature R of a corner portion on the side surface of the container is 1 mm or more.
<3> The container according to any one of <1> to <2>, wherein the crystalline polymer film in the container has a thickness of 30 μm or more and 500 μm or less.
<4> A ratio ((B / A) × 100) of the surface area (A) of the container and the area (B) of the crystalline polymer film in the container is 25% or more <1> to <3> It is a container in any one of.
<5> The container according to any one of <1> to <4>, wherein the crystalline polymer film and the container are integrated.
<6> The container according to <1>, wherein the crystalline polymer film wound around the container is contracted.
<7> The thermal contraction rate at 150 ° C. of the crystalline polymer film is 10% or more in the first direction and 5% or less in the second direction orthogonal to the first direction. The container.
<8> The container according to any one of <6> to <7>, wherein the crystalline polymer film in the container has a thickness of 45 μm or more and 300 μm or less.
<9> The ratio of the surface area (A) of the container to the area (B) of the crystalline polymer film in the container ((B / A) × 100) is 30% or more. <6> to <8> It is a container in any one of.
<10> The container according to any one of <6> to <9>, wherein a transmittance of the crystalline polymer film with respect to light having one wavelength selected from wavelengths of 300 nm to 780 nm is 10% or less.
<11> consisting of a polymer having crystallinity, and placing a crystalline polymer film containing a long cavity inside thereof in a state in which the length direction is oriented in the first direction in a blow mold;
Placing a preform in a blow mold in which the crystalline polymer film is placed;
Blowing the preform,
In the cross section perpendicular to the orientation direction of the cavities in the crystalline polymer film, the ten cavities having the shortest distance from the center of the cavities to the surface of the crystalline polymer film are the crystal from each center. The distance h (i) to the surface of the conductive polymer film is calculated, and the arithmetic average value h (avg) of each calculated distance h (i) satisfies the relationship of the following formula (1): This is a method for manufacturing a container.
h (avg)> T / 100 (1)
However, in said Formula (1), T represents the arithmetic mean value of the thickness in the said cross section, and the ten said cavities are parallel to the arbitrary 1 straight line parallel to the said thickness direction, and the said 1 straight line. And a cavity existing in a region sandwiched by other straight lines located 20 × T apart.
<12> consisting of a polymer having crystallinity, winding a crystalline polymer film containing a long cavity inside thereof in a state in which the length direction is oriented in the first direction;
Shrinking the wound crystalline polymer film,
In the cross section perpendicular to the orientation direction of the cavities in the crystalline polymer film, the ten cavities having the shortest distance from the center of the cavities to the surface of the crystalline polymer film are the crystal from each center. The distance h (i) to the surface of the conductive polymer film is calculated, and the arithmetic average value h (avg) of each calculated distance h (i) satisfies the relationship of the following formula (1): This is a method for manufacturing a container.
h (avg)> T / 100 (1)
However, in said Formula (1), T represents the arithmetic mean value of the thickness in the said cross section, and the ten said cavities are parallel to the arbitrary 1 straight line parallel to the said thickness direction, and the said 1 straight line. And a cavity existing in a region sandwiched by other straight lines located 20 × T apart.

According to the present invention, various conventional problems can be solved, and the container is excellent in strength, light-shielding property, and heat retaining property, and can be easily compressed to reduce the volume, and the container is excellent in recyclability, and the container The manufacturing method of can be provided.

FIG. 1 is a diagram illustrating a state in which a cup-shaped container is held. FIG. 2 is a diagram illustrating a state in which the PET bottle is held. FIG. 3 is a diagram illustrating a state in which a PET bottle is held. FIG. 4A is a diagram for specifically explaining the aspect ratio, and is a perspective view of a crystalline polymer film. FIG. 4B is a diagram for specifically explaining the aspect ratio, and is a cross-sectional view taken along the line A-A ′ of the crystalline polymer film in FIG. 4A. FIG. 4C is a diagram for specifically explaining the aspect ratio, and is a B-B ′ cross-sectional view of the crystalline polymer film in FIG. 4A. FIG. 4D is a cross-sectional view taken along the line A-A ′ in FIG. 4A for explaining a method of measuring the distance from the film surface of ten cavities located closest to the film surface. 5A is a cross-sectional view taken along the line A-A ′ of the crystalline polymer film in FIG. 4A taken with an electron microscope. FIG. 5B is a B-B ′ cross-sectional view of the crystalline polymer film in FIG. 4A taken by an electron microscope. FIG. 6 is a diagram showing an example of a method for producing a crystalline polymer film of the present invention, and is a flow diagram of a biaxially stretched film production apparatus. FIG. 7 is a schematic diagram for explaining the blowing process. FIG. 8A is a diagram showing a crystalline polymer film processed into a fan shape. FIG. 8B is a diagram showing a state in which the crystalline polymer film is attached to a jig. FIG. 8C is a schematic diagram of a blow mold. FIG. 8D is a schematic cross-sectional view of a blow mold. FIG. 9 is a view for explaining the container of Example A-1. FIG. 10 is a diagram illustrating a process of winding the crystalline polymer film around the container of Example A-2. FIG. 11 is a diagram illustrating the shape of the container of Example A-4. FIG. 12 is a view for explaining the shape of the container of Example A-5. FIG. 13 is an explanatory diagram of the design printed in Example A-1. FIG. 14A is a schematic diagram for explaining the measurement of heat resistance. FIG. 14B is a schematic diagram for explaining the measurement of heat resistance. FIG. 14C is a schematic diagram for explaining the measurement of heat resistance. FIG. 15 is a schematic diagram for explaining the container used in Example B-1.

(container)
The container of this invention has a container and a crystalline polymer film at least, and also has another structure as needed.

<Crystalline polymer film>
The crystalline polymer film is made of a polymer having crystallinity, and contains a long cavity in a state where the length direction is oriented in the first direction.

-Polymer with crystallinity-
In general, polymers are classified into crystalline polymers and amorphous (amorphous) polymers, but even polymers with crystallinity are not 100% crystalline, and long chain molecules in the molecular structure. Includes a crystalline region regularly arranged and an amorphous region which is not regularly arranged.
Therefore, the polymer having crystallinity according to the present invention only needs to include at least the crystalline region in the molecular structure, and the crystalline region and the amorphous region may be mixed.

The polymer having crystallinity is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyolefins (for example, low density polyethylene, high density polyethylene, polypropylene, etc.), polyamides (PA) ( For example, nylon-6, etc., polyacetals (POM), polyesters (eg, PET, PEN, PTT, PBT, PPT, PHT, PBN, PES, PBS, etc.), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polyether ether ketones (PEEK), liquid crystal polymers (LCP), fluororesin, isotactic polypropylene (isoPP) and the like. Among these, polyolefins, polyesters, syndiotactic polystyrene (SPS), and liquid crystal polymers (LCP) are preferable, and polyolefins and polyesters are more preferable from the viewpoints of durability, mechanical strength, production, and cost. Two or more kinds of these polymers may be blended or copolymerized.

The polymer having crystallinity does not contain a functional group having high absorption in the ultraviolet region, such as an aromatic ring, for example, in order to reduce the light transmittance in the ultraviolet region of the crystalline polymer film (enhance reflection characteristics). It is preferable. Therefore, aliphatic polyester is particularly preferable among the polyesters.

The melt viscosity of the crystalline polymer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50 Pa · s to 700 Pa · s, more preferably 70 Pa · s to 500 Pa · s, More preferably, it is 80 Pa · s to 300 Pa · s. The melt viscosity of 50 Pa · s to 700 Pa · s is preferred in that the shape of the molten film discharged from the die head during melt film formation is stable and uniform film formation is facilitated. Further, when the melt viscosity is 50 Pa · s to 700 Pa · s, the viscosity at the time of melt film formation becomes appropriate and the extrusion becomes easy, or the melt film at the time of film formation is leveled to reduce unevenness. This is preferable.
Here, the melt viscosity can be measured by a plate type rheometer or a capillary rheometer.

The intrinsic viscosity (IV) of the polymer having crystallinity is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.4 to 1.4, preferably 0.6 to 1.2. More preferred is 0.7 to 1.0. When the IV is 0.4 to 1.4, the strength of the formed film is increased, and this is preferable in that the film can be efficiently stretched.
Here, the IV can be measured by an Ubbelohde viscometer.

The melting point (Tm) of the crystalline polymer is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 40 ° C. to 350 ° C., more preferably 100 ° C. to 300 ° C., and more preferably 100 ° C. More preferred is ~ 260 ° C. The melting point of 40 ° C. to 350 ° C. is preferable in that the shape can be easily maintained in a temperature range expected for normal use, and even without using a special technique required for processing at a high temperature. It is preferable at the point which can form a uniform film.
Here, the melting point can be measured by a differential thermal analyzer (DSC).

--- Polyester resin--
The polyesters (hereinafter referred to as “polyester resins”) mean a general term for polymer compounds having an ester bond as a main bond chain. Therefore, as the polyester resin suitable as the polymer having crystallinity, the exemplified PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PTT (polytrimethylene terephthalate), PBT (polybutylene terephthalate), PPT ( Polycondensation of polypentamethylene terephthalate), PHT (polyhexamethylene terephthalate), PBN (polybutylene naphthalate), PES (polyethylene succinate), PBS (polybutylene succinate), dicarboxylic acid component and diol component All polymer compounds obtained by the reaction are included.

The dicarboxylic acid component is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, oxycarboxylic acids, and polyfunctional acids. Can be mentioned.

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, diphenyldicarboxylic acid, diphenylsulfone dicarboxylic acid, naphthalenedicarboxylic acid, diphenoxyethanedicarboxylic acid, and 5-sodium sulfoisophthalic acid. Acid, diphenyldicarboxylic acid, and naphthalenedicarboxylic acid are preferable, and terephthalic acid, diphenyldicarboxylic acid, and naphthalenedicarboxylic acid are more preferable.

Examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid, eicoic acid, adipic acid, sebacic acid, dimer acid, dodecanedioic acid, maleic acid, and fumaric acid. Examples of the alicyclic dicarboxylic acid include cyclohexane dicarboxylic acid. Examples of the oxycarboxylic acid include p-oxybenzoic acid. Examples of the polyfunctional acid include trimellitic acid and pyromellitic acid. Among the aliphatic dicarboxylic acids and alicyclic dicarboxylic acids, the crystalline polymer film has low transmittance (excellent reflection characteristics) in a wide wavelength range including the ultraviolet region, so that succinic acid, adipic acid, Cyclohexanedicarboxylic acid is preferable, and succinic acid and adipic acid are more preferable.

The diol component is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic diols, alicyclic diols, aromatic diols, diethylene glycol, and polyalkylene glycols. Among these, An aliphatic diol is preferable in that the crystalline polymer film has low transmittance (excellent reflection characteristics) in a wide wavelength range including the ultraviolet region.

Examples of the aliphatic diol include ethylene glycol, propane diol, butane diol, pentane diol, hexane diol, neopentyl glycol, triethylene glycol and the like. Among these, propane diol, butane diol, pentane diol, hexane Diols are particularly preferred.
Examples of the alicyclic diol include cyclohexanedimethanol.
Examples of the aromatic diol include bisphenol A and bisphenol S.

The melt viscosity of the polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50 Pa · s to 700 Pa · s, more preferably 70 Pa · s to 500 Pa · s, and more preferably 80 Pa · s. More preferable is 300 Pa · s. When the melt viscosity is higher, voids are more likely to occur during stretching. However, when the melt viscosity is 50 Pa · s to 700 Pa · s, extrusion becomes easier during film formation, and the resin flow stabilizes and stays. This is preferable in that it becomes difficult and the quality is stabilized. Further, the melt viscosity of 50 Pa · s to 700 Pa · s is preferable in that the drawing tension is appropriately maintained at the time of drawing, and it becomes easy to draw uniformly and is difficult to break. Further, when the melt viscosity is 50 Pa · s to 700 Pa · s or more, it is easy to maintain the form of the melt film discharged from the die head at the time of film formation, and it is possible to stably form or damage the product. It is preferable in that the physical properties are increased.

The intrinsic viscosity (IV) of the polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.4 to 1.4, more preferably 0.6 to 1.2, More preferably, it is 0.7 to 1.0. When the IV is larger, voids are more likely to be generated during stretching. However, when the IV is 0.4 to 1.4, extrusion is easier during film formation, and the resin flow is stable and retention is less likely to occur. It is preferable in that the quality is stabilized. Furthermore, when the IV is 0.4 to 1.4, the stretching tension is appropriately maintained at the time of stretching, so that it is easy to stretch uniformly, and it is preferable in that a load is not easily applied to the apparatus. In addition, when the IV is 0.4 to 1.4, the product is less likely to be damaged, which is preferable in terms of improving physical properties.

The melting point of the polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of heat resistance and film forming property, 70 ° C. to 300 ° C. is preferable, and 90 ° C. to 270 ° C. More preferred.

In addition, as said polyester resin, the said dicarboxylic acid component and the said diol component may respectively superpose | polymerize with 1 type, and may form the polymer, and the said dicarboxylic acid component and / or the said diol component are 2 or more types. A polymer may be formed by copolymerization. Further, as the polyester resin, two or more kinds of polymers may be blended and used.

In the blend of two or more polymers, the polymer added to the main polymer has a melt viscosity and an intrinsic viscosity that are close to those of the main polymer, and the addition amount is smaller when the film is formed or melted. It is preferable in that the physical properties are enhanced during extrusion and the extrusion becomes easy.

In addition, for the purpose of improving the flow characteristics of the polyester resin, controlling light transmittance, and improving the adhesion with the coating solution, a resin other than polyester may be added to the polyester resin.

As described above, the crystalline polymer film can form voids in a simple process even without adding a void forming agent such as inorganic fine particles and incompatible resins added in the prior art. it can. Thereby, the recyclability of the crystalline polymer film can be enhanced. Furthermore, no special equipment for dissolving the inert gas in the resin in advance is required. The method for producing the crystalline polymer film will be described later.

Here, as long as the crystalline polymer film is a component that does not contribute to the development of cavities, it may contain other components other than the polymer having crystallinity as necessary. Examples of the other components include a heat resistance stabilizer, an antioxidant, an organic lubricant, a nucleating agent, a dye, a pigment, a dispersant, and a coupling agent. Whether or not the other component contributed to the development of the cavity can be determined by whether or not a component other than the polymer having crystallinity (for example, each component described later) is detected in the cavity or at the interface portion of the cavity. .

There is no restriction | limiting in particular as said antioxidant, According to the objective, it can select suitably, For example, you may add well-known hindered phenols. Examples of the hindered phenols include antioxidants commercially available under trade names such as Irganox 1010, Sumilyzer BHT, Sumilyzer GA-80.
Further, the antioxidant can be used as a primary antioxidant and further combined with a secondary antioxidant. Examples of the secondary antioxidant include antioxidants commercially available under trade names such as Sumilizer TPL-R, Sumilizer TPM, Sumilizer TP-D, and the like.

The fluorescent brightening agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, commercially available products with trade names such as Ubitech, OB-1, TBO, Keicoal, Kayalite, Leukopua, EGM, etc. Can be used. In addition, the said fluorescent whitening agent may be used individually by 1 type, and may use 2 or more types together. By adding the fluorescent whitening agent in this way, it is possible to give a brighter and more bluish whiteness and to have a high-class feeling.

-cavity-
The crystalline polymer film contains elongated cavities inside with the length direction oriented in one direction, and is characterized by the cavity content and aspect ratio of the cavities.
The cavity means a domain in a vacuum state or a gas phase domain existing inside the crystalline polymer film.

The void content means the total volume of the contained cavities relative to the sum of the total volume of the solid phase portion of the crystalline polymer film and the total volume of the contained cavities.
The void content is not particularly limited as long as the effects of the present invention are not impaired, can be appropriately selected according to the purpose, and is preferably 3% by volume to 50% by volume, and 5% by volume to 40% by volume. More preferably, 10% by volume to 30% by volume is even more preferable.
Here, the void content can be calculated based on the specific gravity by measuring the specific gravity.
Specifically, the void content can be obtained by the following equation (2).
Cavity content (%) = {1− (density of crystalline polymer film after stretching) / (density of polymer molded body before stretching)} (2)

The aspect ratio refers to an average length of the cavity in the thickness direction orthogonal to the orientation direction of the cavity, r (μm), and an average length of the cavity in the orientation direction of the cavity, L (μm). L / r ratio is meant.
The aspect ratio is not particularly limited as long as the effects of the present invention are not impaired, and can be appropriately selected according to the purpose. The aspect ratio is preferably 10 or more, more preferably 15 or more, and still more preferably 20 or more.

4A to 4C are diagrams for specifically explaining the aspect ratio. FIG. 4A is a perspective view of the crystalline polymer film, and FIG. 4B is an A diagram of the crystalline polymer film in FIG. 4A. FIG. 4C is a cross-sectional view taken along the line −A ′, and FIG. 4C is a cross-sectional view taken along the line BB ′ of the crystalline polymer film in FIG. 4A.

In the manufacturing process of the crystalline polymer film, the cavities are usually oriented along the first stretching direction. Therefore, the “average length (r (μm) of the cavities in the thickness direction orthogonal to the orientation direction of the cavities)” is perpendicular to the surface 1a of the crystalline polymer film 1 and in the first stretching direction. This corresponds to the average thickness r (see FIG. 4B) of the cavity 100 in a cross section at right angles (cross section AA ′ in FIG. 4A). Further, “the average length of the cavities (L (μm)) in the orientation direction of the cavities” is a cross section perpendicular to the surface 1a of the crystalline polymer film 1 and parallel to the first stretching direction ( This corresponds to the average length L (see FIG. 4C) of the cavity 100 in the BB ′ cross section in FIG. 4A.

In addition, said 1st extending | stretching direction shows the extending direction of 1 axis | shaft, when extending | stretching is only 1 axis | shaft. Usually, since longitudinal stretching is performed along the direction in which the molded body flows during production, this longitudinal stretching direction corresponds to the first stretching direction.
Moreover, when extending | stretching is biaxial or more, at least 1 direction is shown among the extending directions aiming at cavity formation. Usually, even in stretching with two or more axes, longitudinal stretching is performed along the flow direction of the molded body during production, and a cavity can be formed by this longitudinal stretching. It corresponds to the first stretching direction.

Here, the average length (r (μm)) of the cavities in the thickness direction perpendicular to the alignment direction of the cavities can be measured by an image of an optical microscope or an electron microscope. Similarly, the average length (L (μm)) of the cavities in the alignment direction of the cavities can be measured by an image of an optical microscope or an electron microscope.

The average number P of the cavities in the thickness direction perpendicular to the orientation direction of the cavities is not particularly limited and can be appropriately selected according to the purpose, preferably 5 or more, more preferably 10 or more, 15 or more are more preferable.

In the manufacturing process of the crystalline polymer film, the cavities are usually oriented along the first stretching direction. Therefore, the “number of the cavities in the thickness direction orthogonal to the orientation direction of the cavities” is a cross section perpendicular to the surface 1a of the crystalline polymer film 1 and perpendicular to the first stretching direction (A in FIG. 4A). This corresponds to the number of cavities 100 included in the film thickness direction in (−A ′ cross section).
Here, the average number P of the cavities in the thickness direction orthogonal to the orientation direction of the cavities can be measured by an image of an optical microscope or an electron microscope.

An example of a cross-sectional view of the crystalline polymer film of the present invention is shown in FIGS. 5A and 5B.
FIG. 5A is a cross-sectional view taken along the line AA ′ of the crystalline polymer film in FIG. 4A taken with an electron microscope. FIG. 5B is a BB ′ cross-sectional view of the crystalline polymer film in FIG. 4A taken with an electron microscope.
The cross-sectional view of the crystalline polymer film of the present invention is not limited to FIGS. 5A and 5B.

The refractive index difference ΔN between the crystalline polymer layer and the cavity layer is specifically the refractive index of the cavity layer with respect to light with a wavelength of 589 nm, where N1 is the refractive index of the polymer layer with crystallinity with respect to light with a wavelength of 589 nm. Is the value of ΔN (= N1−N2) which is the difference between N1 and N2.
Here, the refractive indices N1 and N2 of the crystalline polymer layer and the cavity layer can be measured by an Abbe refractometer or the like.
The product of ΔN and P is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 or more, more preferably 5 or more, and still more preferably 7 or more.

Furthermore, the crystalline polymer film has excellent surface smoothness because it contains the voids but is not added with inorganic fine particles, incompatible resin, inert gas, etc. for expressing the voids. Have.
The surface smoothness of the crystalline polymer film is not particularly limited and may be appropriately selected according to the purpose. However, Ra = 0.3 μm or less is preferable, Ra = 0.25 μm or less is more preferable, and Ra = 0.1 μm or less is particularly preferable.

As described above, the crystalline polymer film has various excellent characteristics in terms of, for example, heat shrinkage rate, light transmittance, heat insulating property, strength, and the like due to the inclusion of the cavities. In other words, characteristics such as heat shrinkage rate, light transmittance, heat insulating property, strength, etc. can be adjusted by changing the mode of the cavities contained in the crystalline polymer film.

Further, the crystalline polymer film is characterized in that no cavity is formed not only on the film surface but also at a predetermined distance from the film surface.
That is, in the cross section perpendicular to the orientation direction of the cavities in the crystalline polymer film, the ten cavities having the shortest distance from the center of the cavities to the surface of the crystalline polymer film are separated from each center. The distance h (i) to the surface of the crystalline polymer film is calculated, and the calculated arithmetic average value h (avg) of each distance h (i) satisfies the relationship of the following formula (1).
h (avg)> T / 100 (1)
However, in said Formula (1), T represents the arithmetic mean value of the thickness in the said cross section, and the ten said cavities are parallel to the arbitrary 1 straight line parallel to the said thickness direction, and the said 1 straight line. And a cavity existing in a region sandwiched by other straight lines located 20 × T apart.

The “center of the cavity” means the center when the cross-sectional shape of the cavity in the cross section is a perfect circle, and is arbitrarily set by, for example, the maximum square center method in the case of other shapes. The center of the circle that minimizes the sum of squares of the deviation from the reference circle is determined, and this is set as the center of the cavity.
The “surface of the crystalline polymer film” means the outermost surface of the crystalline polymer film in the thickness direction. Usually, it means the upper surface when the crystalline polymer film is placed.

Specifically, a cross-section (see FIG. 4D) perpendicular to the surface of the crystalline polymer film and perpendicular to the longitudinal stretching direction (see FIG. 4D) is appropriately magnified 300 to 3000 times using a scanning electron microscope. Microscope and take a cross-sectional picture. In the cross-sectional photograph, an arithmetic average value T of the thickness is calculated. As the arithmetic average value T of the thickness, a thickness measured using a long range contact displacement meter or the like may be used.
Next, an arbitrary straight line parallel to the thickness direction is drawn in the cross-sectional photograph, and another straight line that is parallel to the single straight line and separated by 20 × T is drawn.
Then, in each cavity in the cross-sectional photograph, the center of a circle that minimizes the sum of squares of deviations from the reference circle arbitrarily set by the maximum square center method is determined, and this is set as the center of the cavity.
Then, ten cavities having the shortest distance from the center of the cavity to the surface of the crystalline polymer film are selected in a region sandwiched between the one straight line and the other straight line. Note that the “distance from the center of the cavity to the surface of the crystalline polymer film” means that when drawing a circle centered on the “center of the cavity”, the radius of the circle to be drawn is sequentially increased, The radius of the circle when it first contacts the surface of the crystalline polymer film.
Then, for the 10 selected cavities, a distance h (i) from each center to the surface of the crystalline polymer film is calculated, and an arithmetic average value h (avg) of each calculated distance h (i) Is calculated by the following equation (3).
h (avg) = (Σh (i)) / 10 (3)
The “distance h (i) from each center to the surface of the crystalline polymer film” should be accurately measured when the crystalline polymer film is curved or stressed. Therefore, it is preferable that the measurement is performed in a state where it is placed in a flat shape.
Although the said crystalline polymer film contains the said cavity, since the cavity is not formed near the surface of the crystalline polymer film, it has the outstanding surface smoothness.

-Light transmittance-
The light transmittance of the crystalline polymer film is the light intensity of transmitted light / light intensity of incident light when light of a predetermined wavelength is incident perpendicularly to the surface of the crystalline polymer film × 100. It means the value of (%).

The transmittance of the crystalline polymer film with respect to light having one wavelength selected from wavelengths of 300 nm to 780 nm (light transmittance) is not particularly limited as long as the effect of the present invention is not impaired, and depends on the purpose. Although it can select suitably, 10% or less is preferable, 5% or less is more preferable, 4% or less is further more preferable, and 3% or less is especially preferable.

The crystalline polymer film has the same thickness as that of the crystalline polymer film, where M _λ (%) is a transmittance with respect to light having one wavelength selected from wavelengths of 300 nm to 780 nm. M when the transmittance of light of the selected wavelength, which is made of a polymer having the same crystallinity as the polymer having the crystallinity constituting the film and does not contain a cavity, is N _λ (%) _{The λ} / _Nλ ratio is preferably 0.2 or less, more preferably 0.18 or less, and still more preferably 0.15 or less.
Here, the transmittance can be measured by a spectrophotometer.

As described above, the crystalline polymer film has a low transmittance (high reflectance) in the ultraviolet region (300 nm to 380 nm), and further has a low transmittance (high reflectance) in the ultraviolet region. However, it has low transmittance (excellent reflection characteristics) even in the visible region (380 nm to 780 nm). The low transmittance (excellent reflection characteristic) of the crystalline polymer film is due to the structural optical interference between multiple layers formed inside the crystalline polymer film consisting of a cavity layer and a crystalline polymer layer. by. In other words, the reflection characteristics such as the transmittance can be adjusted by changing the mode (aspect ratio, refractive index, etc.) of the cavities contained in the crystalline polymer film.

-Thickness-
There is no restriction | limiting in particular as thickness of the said crystalline polymer film, According to the objective, it can select suitably.
In the container of the present invention, when the crystalline polymer film is wound and is not shrunk, the thickness of the crystalline polymer film is preferably 30 μm to 500 μm, more preferably 50 μm to 300 μm, and more preferably 80 μm. Particularly preferred is ˜150 μm. When the thickness of the crystalline polymer film is less than 30 μm, there is a concern that the container cannot be held by hand, and when it exceeds 500 μm, it may not be possible to smoothly fit the container. On the other hand, when the thickness of the crystalline polymer film is within the particularly preferable range, it is advantageous in that a sufficient function as a container can be expressed.
In the container of the present invention, when the crystalline polymer film is wound and contracted (shrinked), the thickness of the crystalline polymer film is preferably 45 μm to 300 μm, more preferably 80 μm to 200 μm. 80 μm to 120 μm is particularly preferable. If the thickness of the crystalline polymer film is less than 45 μm, the strength may be insufficient and the film may be easily deformed, and the generation of voids may not be stable, making it difficult to obtain sufficient reflection and light shielding functions. When the thickness exceeds 300 μm, it is difficult to obtain a uniform film, processing becomes difficult, and wrinkles are likely to occur. On the other hand, when the thickness of the crystalline polymer film is within the particularly preferable range, it is advantageous in that it can be easily processed and a sufficient function can be obtained.

-Thermal shrinkage-
The heat shrinkage rate of the crystalline polymer film is a sample obtained by cutting the crystalline polymer film into a 100 mm square and heat-treating the sample in an oven adjusted to a predetermined temperature for 10 minutes. It means a value measured and determined according to the following formula.

The heat shrinkage rate at 150 ° C. in the first direction of the crystalline polymer film is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10% or more, more preferably 12% or more. Preferably, 15% or more is more preferable. The “first direction” means the first stretching direction (FIG. 4A).
The heat shrinkage rate at 150 ° C. in the second direction orthogonal to the first direction of the crystalline polymer film is not particularly limited and can be appropriately selected according to the purpose. It is preferably 4% or less, more preferably 3% or less.

-Method for producing crystalline polymer film-
The method for producing the crystalline polymer film is not particularly limited and may be appropriately selected depending on the intended purpose. However, it preferably includes at least a stretching step of stretching the polymer molded body 2 to 10 times. By including the said extending | stretching process, the shrinkability of the crystalline polymer film obtained can be improved. The method for producing the crystalline polymer film may further include other steps such as a film forming step as necessary.
In addition, the said polymer molded object shows the thing which consists of a polymer which has the said crystallinity, and does not contain a cavity especially, for example, a polymer film, a polymer sheet, etc. are mentioned.

--Stretching process--
In the stretching step, the polymer molded body is stretched at least uniaxially. Then, by the stretching step, the polymer molded body is stretched, and a cavity oriented along the first stretching direction is formed therein, whereby a crystalline polymer film is obtained.

The reason why the cavity is formed by stretching is that the polymer having at least one crystallinity constituting the polymer molded body has a microcrystalline domain or a crystalline domain, and a microcrystal or crystal that is difficult to stretch during stretching. It is considered that the cavity is formed by being peeled and stretched in such a manner that the amorphous phase and the resin in the amorphous portion are torn off.
Such void formation by stretching is possible not only when there is only one kind of polymer having crystallinity but also when two or more kinds of polymers having crystallinity are blended or copolymerized. is there.

The stretching method is not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include uniaxial stretching, sequential biaxial stretching, and simultaneous biaxial stretching. It is preferable that longitudinal stretching is performed along the direction in which the molded body flows.

In general, in the longitudinal stretching, the number of longitudinal stretching stages and the stretching speed can be adjusted by the combination of rolls and the speed difference between the rolls.
The number of stages of the longitudinal stretching is not particularly limited as long as it is one or more, but it can be stretched more than two stages in terms of more stable and high-speed stretching and production yield and machine restrictions. It is preferable to do. Further, longitudinal stretching in two or more stages is advantageous in that a cavity can be formed by stretching in the second stage after confirming the occurrence of necking in the first stage.

--Stretching speed--
The stretching speed of the longitudinal stretching is not particularly limited as long as the effects of the present invention are not impaired, and can be appropriately selected according to the purpose, but is preferably 10 mm / min to 36,000 mm / min, and preferably 800 mm / min. Is more preferably 24,000 mm / min, and further preferably 1,200 mm / min to 12,000 mm / min. When the stretching speed is 10 mm / min or more, it is preferable in that sufficient necking can be easily expressed. Further, when the stretching speed is 36,000 mm / min or less, uniform stretching is facilitated, the resin is not easily broken, and the cost is reduced without requiring a large stretching apparatus for high-speed stretching. It is preferable in that it can be performed. Therefore, when the stretching speed is 10 mm / min to 36,000 mm / min, sufficient necking is easily exhibited, uniform stretching is facilitated, the resin is not easily broken, and high speed stretching is intended. This is preferable in that the cost can be reduced without requiring a large stretching apparatus.

More specifically, the stretching speed in the case of one-stage stretching is preferably 1,000 mm / min to 36,000 mm / min, more preferably 1,100 mm / min to 24,000 mm / min, and 1,200 mm / min. More preferably, it is from min to 12,000 mm / min.

In the case of two-stage stretching, it is preferable that the first-stage stretching is a preliminary stretching whose main purpose is to develop necking. The stretching speed of the preliminary stretching is preferably 10 mm / min to 300 mm / min, more preferably 40 mm / min to 220 mm / min, and still more preferably 70 mm / min to 150 mm / min.

In the two-stage stretching, the second-stage stretching speed after the necking is expressed by the preliminary stretching (first-stage stretching) is preferably changed from the stretching speed of the preliminary stretching. The second stage stretching speed after causing necking by the preliminary stretching is preferably 600 mm / min to 36,000 mm / min, more preferably 800 mm / min to 24,000 mm / min, and 1,200 mm. / Min to 15,000 mm / min is more preferable.

--Extension temperature--
The temperature during stretching is not particularly limited and can be appropriately selected according to the purpose.
When the stretching temperature is T (° C) and the glass transition temperature is Tg (° C),
(Tg-30) (° C.) ≦ T (° C.) ≦ (Tg + 70) (° C.)
It is preferable to stretch at a stretching temperature T (° C.) in the range indicated by
(Tg-25) (° C) ≦ T (° C) ≦ (Tg + 70) (° C)
It is more preferable to stretch at a stretching temperature T (° C.) in the range indicated by
(Tg−20) (° C.) ≦ T (° C.) ≦ (Tg + 70) (° C.)
More preferably, the film is stretched at a stretching temperature T (° C.) in the range indicated by.

Generally, the higher the stretching temperature (° C.), the lower the stretching tension, and the easier the stretching. However, the stretching temperature (° C.) is {glass transition temperature (Tg) −30} ° C. or higher, {glass transition temperature ( Tg) +70} ° C. or lower is preferable in that the void content increases, the aspect ratio tends to be 10 or more, and the voids are sufficiently developed.
Here, the stretching temperature T (° C.) can be measured with a non-contact thermometer. The glass transition temperature Tg (° C.) can be measured by a differential thermal analyzer (DSC).

In the stretching step, lateral stretching may or may not be performed as long as it does not hinder the appearance of cavities. In the case of lateral stretching, the film may be relaxed or heat-treated using a lateral stretching process.
Further, the stretched void-containing resin molded body may be further subjected to treatment such as heat shrinkage by applying heat or applying tension for the purpose of shape stabilization.

The method for producing the polymer molded body is not particularly limited and may be appropriately selected depending on the intended purpose. For example, when the polymer having crystallinity is a polyolefin, a polyester resin, or a polyamide, it is melted. It can be suitably manufactured by a film forming method.
Moreover, the polymer molded body may be produced independently of the stretching step or continuously.

FIG. 6 is a diagram showing an example of a method for producing a crystalline polymer film of the present invention, and is a flow diagram of a biaxially stretched film production apparatus.
As shown in FIG. 6, after the raw material resin 11 is hot-melted and kneaded inside the extruder 12 (a twin screw extruder or a single screw extruder is used depending on the raw material shape and production scale). , And discharged from the T-die 13 in a soft plate shape (film or sheet shape).
Next, the discharged film or sheet F is cooled and solidified by the casting roll 14 to form a film. The formed film or sheet F (corresponding to “polymer molded body”) is sent to the longitudinal stretching machine 15.
And the film or sheet | seat F formed into a film is again heated within the longitudinal stretch machine 15, and is stretched | stretched longitudinally between the rolls 15a from which speed differs. By this longitudinal stretching, a cavity is formed in the film or sheet F along the stretching direction. The film or sheet F in which the cavity is formed is gripped at both ends by the left and right clips 16a of the transverse stretching machine 16, and is stretched laterally while being sent to the winder side (not shown). The polymer film 1 is obtained. In addition, in the said process, you may use the film or sheet | seat F which performed only the longitudinal stretch as the crystalline polymer film 1, without providing to the transverse stretcher 16. FIG.

<Container>
There is no restriction | limiting in particular as said container, According to the objective, it can select suitably.
Examples of the container include a take-out coffee that is poured into a cup at a store. Containers having no irregularities on the surface of these containers are advantageous in that the crystalline polymer film can be easily wound in the manufacture of containers by insert blow molding described later. Furthermore, if the surface has no irregularities and the shape is simple, there is an advantage that less material is required and manufacturing costs can be reduced. If the shape is simple, it can be stacked compactly, and can be transported and stored efficiently, and there is also an advantage that a special technique is not required when applying printing or other design. If the shape is simple, it can be held well without being aware of how to hold it, and it is less likely to cause trouble when handled by babies, infants and the elderly.
Examples of the container include food containers such as soy sauce, dressing, sprinkle, seasoned seaweed, tempura oil, and beverages such as milk, lactic acid bacteria beverages, beer, shochu, wine, vitamin beverages, juices, carbonated beverages, water, and tea. Containers, makeup removers, lotions, skin care, sunscreens, whitening, facial cleansing, moisturizing, cosmetic containers such as cosmetics, body, pet, clothing, industrial detergent containers and the like. In the case where the crystalline polymer film is wound and contracted (shrink), among these, a container having an uneven portion on the surface of a container such as a beverage container is easy to shrink the crystalline polymer film. Is advantageous.

-Radius of curvature R-
There is no restriction | limiting in particular as the curvature radius R of the corner | angular part of the said container side surface, Although it can select suitably according to the objective, 1 mm or more is preferable, 2 mm or more is more preferable, and 5 mm or more is especially preferable. If the curvature radius R is less than 1 mm, the cavity of the bent portion may be crushed and the function of the film may be difficult to be exhibited. On the other hand, when the radius of curvature R is within the particularly preferable range, it is advantageous in that the film performance can be sufficiently exhibited after molding.
The radius of curvature R can be measured by, for example, a three-dimensional shape measuring apparatus XYZAX RA1600A (manufactured by Tokyo Seimitsu Co., Ltd.).
Here, whether or not the cavity in the crystalline polymer film at the corner has been crushed can be confirmed as follows. For example, after embedding and cutting out the site | part which wants to observe, the cross section can be observed and confirmed with an electron microscope.

(Manufacturing method of container)
There is no restriction | limiting in particular as a manufacturing method of the container of this invention, According to the objective, it can select suitably, For example, the method (henceforth "the 1st" which winds the said crystalline polymer film around the shape | molded container. ), An insert blow molding method in which the crystalline polymer film is wound together with the molding of the container (hereinafter, sometimes referred to as “second aspect”), a winding step, And a method including at least a contraction (shrink) step (hereinafter, may be referred to as a “third aspect”).
Among these, when the crystalline polymer film is wound and does not shrink (shrink), the insert blow molding method integrates the crystalline polymer film and the container to produce a container having excellent strength. This is advantageous in that it can be done.

<First aspect>
The first aspect includes at least a winding step, and further includes other steps as necessary.

-Winding process-
The winding step is a step of winding the crystalline polymer film around a molded container.

The shape, size and material of the molded container are not particularly limited and can be appropriately selected according to the purpose.

The method for winding the crystalline polymer film around the container is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a film that has been processed into a cylindrical shape in advance is placed on the container, For example, after winding directly, the winding end is cut and heat-sealed or glued.

<Second aspect>
In the second aspect, a crystalline polymer film is disposed in a blow mold (hereinafter sometimes referred to as “crystalline polymer film disposing step”), and the crystalline polymer film is disposed. A step of placing a preform on the mold (hereinafter, sometimes referred to as “preform placement step”) and a step of blowing the preform (hereinafter, also referred to as “blowing step”). Including at least, and further including other steps as necessary.
The second aspect is also referred to as insert blow molding. In the insert blow molding, when a preform (also referred to as a parison) is set in a blow mold, the crystalline polymer film is attached in advance to the inner wall of the blow mold, and in the subsequent blow step, the preform is molded. Reform swells. This is a method for producing a container, in which the crystalline polymer film is attached to the outer surface of a resin molded body (blow molded product) that sticks to the inner wall of the mold to obtain a container having a design and other functions.

-Crystalline polymer film placement process-
The crystalline polymer film arranging step is a step of arranging the crystalline polymer film in a blow mold.

--Blow mold--
There is no restriction | limiting in particular as a shape, a magnitude | size, and a material of the said blow die, According to the objective, it can select suitably.
The blow mold is usually divided into two or more members in order to take out the container (molded product) after the molding is completed in the blow process described later (in FIG. 7, it is divided into two parts).

--- Arrangement--
There is no restriction | limiting in particular as a method of arrange | positioning the said crystalline polymer film in the said blow die, According to the objective, it can select suitably.
An example of a method for disposing the crystalline polymer film in the blow mold will be described with reference to FIGS. 8A to 8D.
FIG. 8A is a diagram showing a crystalline polymer film 41 processed into a fan shape. The crystalline polymer film 41 is attached to a jig 42 (see FIG. 8B). The jig 42 preferably has substantially the same angle as the inner wall of the blow mold (or an angle that allows a slight gap at the lower end when set on the blow mold). In FIG. 8B, reference numeral 46 denotes a suction hole, and the crystalline polymer film 41 can be brought into close contact with the jig 42 by suction in the direction of the arrow.
The jig 42 to which the crystalline polymer film 41 is brought into close contact with the crystalline polymer film 41 from the bottom of the blow mold (closed) while keeping the crystalline polymer film 41 in close contact with the inside of the mold. Insert into.
As shown in FIG. 8C, the blow mold 43 is provided with a slit 44 for air suction, whereby the suction of the jig 42 is stopped after the crystalline polymer film 41 is sucked, and the jig is stopped. The tool 42 is removed from the blow mold.
Thereby, the crystalline polymer film 41 can be disposed in the blow mold.
FIG. 8D is a schematic cross-sectional view of the blow mold 43. Reference numeral 45 indicates a suction nozzle, and an arrow indicates a suction direction.

It is preferable to apply an adhesive to the crystalline polymer film.
The adhesive is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a heat-sensitive adhesive used for a hot stamp thermal transfer film, a hot-melt adhesive that is activated at a heating temperature in a blow process described later. Agents and the like.
Examples of the heat-sensitive adhesive used for the hot stamp thermal transfer film include cyclized rubber resins, acrylic resins, vinyl chloride resins, and vinyl acetate resins.
Examples of the hot melt adhesive that is activated at the heating temperature in the blowing step include ethylene-vinyl acetate copolymer (EVA), polyethylene, atactic polypropylene (APP), ethylene-ethyl acrylate copolymer (EEA), and polyamide. And those having a base polymer such as polyester, and tackifiers compatible with these base polymers include rosin and derivatives thereof, pinene polymers, and waxes.
There is no restriction | limiting in particular as an application quantity of the said adhesive agent, According to the goods form of a container, compatibility and adhesiveness are adjusted so that desired sticking strength may be obtained. Thereby, the said crystalline polymer film can also be made easy to peel from the container after use.

-Preform placement process-
The preform placement step is a step of placing a preform on a mold on which the crystalline polymer film is placed.

--preform--
There is no restriction | limiting in particular as a material of the said preform (it is also called parison), a shape, and a magnitude | size, According to the objective, it can select suitably.
There is no restriction | limiting in particular as a manufacturing method of the said preform, For example, the injection molding method is mentioned.

--- Arrangement--
There is no restriction | limiting in particular as a method of arrange | positioning the said preform in the said blow metal mold | die, According to the objective, it can select suitably.
When the preform is preheated, it is preferable that the preform is quickly placed in the blow mold after the temperature of the body portion of the preform reaches a predetermined temperature.

The preform may be preheated before being placed in the blow mold.
The temperature of the preheating is not particularly limited and is appropriately selected depending on the type of resin used for the preform, the crystallinity of the preform, the crystal size of the preform, the thickness of the preform, the shape of the preform, and the like. For example, in the case of PET resin, it may be heated at about 90 ° C. to 110 ° C.
There is no restriction | limiting in particular as the method of the said preheating, According to the objective, it can select suitably, For example, an infrared panel heater is mentioned.
The preferred temperature for the preheating can be determined by performing a heating test while measuring the temperature of the preform body with a non-contact thermometer or the like.

-Blow process-
The blowing step is a step of blowing the preform to form a container.
FIG. 7 is a schematic diagram for explaining the blowing process.
In the blowing step, high pressure air is introduced into the preform from the air flow path 59 into the preform 55 arranged in the

blow molds

51 and 52, and blow is performed. Thereby, the container of the shape along the shape inside a blow die can be obtained.

During the blowing, stretching (longitudinal stretching) using the stretching rod 58 may be performed in order to stably obtain the shape of the molded body (container) or as necessary. The stretching using the stretching rod 58 may be performed before high-pressure air is introduced, or may be performed simultaneously with the introduction of high-pressure air.
The stretching rod 58 of FIG. 7 has a stretching rod head 54 at the tip. There is no restriction | limiting in particular as a shape of the said extending | stretching rod head, According to the objective, it can select suitably, For example, the convex shape which is round upwards is mentioned.
FIG. 7 shows a state in which the stretching rod head 54 pushes up the inner wall of the front end of the preform 55. Before the stretching rod 58 rises, the stretching rod head 54 is lowered to the position just above the base, and the front end of the preform 55 The inner wall and the extending rod head 54 are not in contact.
The stretching rod can be lifted by a hydraulic cylinder, for example. The speed at which the hydraulic cylinder is lifted (the speed at which the preform is stretched) is not particularly limited as long as stretch blow can be performed, and can be appropriately selected according to the purpose, but is 10 cm / 0.1 sec to 10 cm / About 2 sec is preferable in that the preform extends without unevenness.
The distance for lifting the stretching rod is not particularly limited and can be appropriately selected depending on the purpose. However, the blow mold ceiling (the bottom of the blow molded body is formed from the surface of the base 56 of the blow mold). To 50% to 80% of the distance to the portion.
In addition, as shown in FIG. 7, the opening part of a blow molded object has faced down (base side of a blow mold).
In FIG. 7, reference numeral 53 denotes a crystalline polymer film, reference numeral 56 denotes a base, and reference numeral 57 denotes a guide.

The pressure of the high-pressure air is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.5 MPa to 4 MPa, more preferably 1 MPa to 3 MPa, and particularly preferably 1 MPa to 2 MPa. If the pressure is less than 0.5 MPa, it may not be able to swell sufficiently, and if it exceeds 4 MPa, it is difficult to blow uniformly, and the container may be broken during blowing. On the other hand, when the pressure is within the particularly preferable range, it is advantageous in that the container can be stably inflated.
The temperature of the high-pressure air is not particularly limited, and is appropriately selected according to the type of resin used in the preform, the crystallinity of the preform, the crystal size of the preform, the thickness of the preform, the shape of the preform, etc. For example, 60 degreeC is mentioned.

In the case of the container of the present invention, when the crystalline polymer film is wound and does not shrink (shrink), it can be suitably manufactured according to the first aspect and the second aspect.
In the container of the present invention, when the crystalline polymer film is wound and is not shrunk, it is preferable that the crystalline polymer film and the container are integrated.

In the container of the present invention, when the crystalline polymer film is wound and not contracted (shrinked), the number of laminated crystalline polymer films is not particularly limited and can be appropriately selected according to the purpose. However, 1 to 10 sheets are preferable, and 1 to 5 sheets are more preferable. When the number of laminated layers is 10 or more, the number of pretreatment steps such as adhesion when laminating increases, and it becomes difficult to make a homogeneous film. In addition, the laminated film becomes thick and the flexibility becomes low, and alignment may be difficult when set in a mold.

The thickness of the crystalline polymer film in the case where the crystalline polymer film is wound and not contracted (shrinked) in the container of the present invention is not particularly limited and can be appropriately selected depending on the purpose. 30 μm to 500 μm is preferable, 80 μm to 300 μm is more preferable, and 100 μm to 200 μm is particularly preferable. If the thickness of the crystalline polymer film in the container is less than 30 μm, the film may wrinkle during insert molding, and if it exceeds 500 μm, it may be attached to a jig when set in the mold. It may be difficult to attach. On the other hand, when the thickness of the crystalline polymer film in the container is within the particularly preferable range, it is advantageous in that the film can be easily set at a predetermined position.

The ratio of the surface area (A) of the container and the area (B) of the crystalline polymer film in the container when the crystalline polymer film is not wound and contracted (shrink) in the container of the present invention ((B / A) × 100) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 25% or more, more preferably 67% or more, and particularly preferably 80% or more. When the ratio is less than 25%, since the ratio of the surface covered with the film is small, the container is easily deformed, and the film performance may not be sufficiently exhibited. On the other hand, when the ratio is within the particularly preferable range, it is advantageous not only that the container is hardly deformed but also that the performance of the film can be sufficiently exhibited.

The arrangement of the crystalline polymer film in the case of winding the crystalline polymer film in the container of the present invention and not shrinking (shrinking) is not particularly limited and can be appropriately selected according to the purpose. For example, it is preferably used on the side of the container in terms of strength, heat insulation, design, and the like.

<Third Aspect>
The third aspect includes at least a winding step and a contraction (shrink) step, and further includes other steps as necessary.
According to the third aspect, the container of the present invention in which the crystalline polymer film is wound and contracted (shrinked) can be suitably manufactured.

-Shrink process-
The shrinking step is a step of shrinking (shrinking) the wound crystalline polymer film.

There is no restriction | limiting in particular as the method of the said shrink (shrink), According to the objective, it can select suitably, For example, a flame, steam, hot water, a hot air, a far-infrared heater, a carbon dioxide laser, etc. are mentioned.
There is no restriction | limiting in particular as an apparatus used for the said shrink, According to the objective, it can select suitably, For example, the method of letting the said product pass through a heated tunnel, etc., the shrink tunnel IST of Horiko Co., Ltd. -780EF, etc.

The thickness of the crystalline polymer film in the container of the present invention obtained by winding and shrinking (shrinking) the crystalline polymer film obtained as described above is not particularly limited and can be appropriately selected depending on the purpose. However, it is preferably 45 μm to 300 μm, more preferably 80 μm to 200 μm, and particularly preferably 80 μm to 120 μm. If the thickness of the crystalline polymer film in the container is less than 45 μm, the strength may be insufficient and the film may be easily deformed, or the generation of voids may not be stable, and it may be difficult to obtain sufficient reflection and light shielding functions. If it exceeds 300 μm, it may be difficult to process and wrinkles may occur. On the other hand, when the thickness of the crystalline polymer film in the container is within the particularly preferable range, it is advantageous in that the workability is excellent and a sufficient function can be expressed.

The ratio of the surface area (A) of the container and the area (B) of the crystalline polymer film in the container ((B / A)) in the container wound and contracted (shrinked). There is no restriction | limiting in particular as (x100), Although it can select suitably according to the objective, 30% or more is preferable, 50% or more is more preferable, and 70% or more is especially preferable. When the ratio is less than 30%, the effect of the shrink film of the present invention may be reduced. On the other hand, when the ratio is within the particularly preferable range, it is advantageous in that the effect of the shrink film of the present invention can be sufficiently exhibited.

Further, the arrangement of the crystalline polymer film in a container in which the crystalline polymer film is wound and contracted (shrinked) is not particularly limited and can be appropriately selected depending on the purpose. A neck portion near the lid, a bottom portion of the container, and the like. Among these, the trunk portion of the container is preferable in that the shrink treatment is easily performed uniformly and the shrink film is less likely to be wrinkled. Further, the barrel portion occupies a large area of the container and is preferable in that the effect of winding the film is easily obtained.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are not intended to limit the present invention, and modifications may be made without departing from the spirit described above and below. Included in the technical scope.

(Production Example A-1-1)
PBT (polybutylene terephthalate 100% resin) having an intrinsic viscosity (IV) = 0.72 is extruded on a casting melt extruder with a coat hanger type die head at 255 ° C. and cooled to 15 ° C. And a polymer film having a thickness of 0.5 mm was obtained.
This polymer film was uniaxially stretched (longitudinal stretching). Specifically, necking stretching (uniaxial) was performed at a speed of 6,000 mm / min in a heated atmosphere of 42 ° C.
The polymer molded body (polymer film) was stretched 5.2 times by the one-stage uniaxial stretching.
Thus, the crystalline polymer film of Production Example A-1-1 was produced. The crystalline polymer film had a thickness of 120 μm, had voids, and exhibited a metallic luster. The film had no voids at a depth of 4 μm to 10 μm from the film surface, and the porosity (the ratio of the cavity volume to the total volume) was 23%.
FIG. 5A is a cross-sectional view taken along the line AA ′ of the crystalline polymer film in FIG. 4A, taken with an electron microscope of the crystalline polymer film of Production Example A-1-1, and the crystalline polymer film in FIG. 4A. FIG. 5B shows a cross-sectional view of BB ′.
In addition, although the said draw ratio generally refers to the speed difference of an extending | stretching roll by roll to roll extending | stretching, in the case of necking extending | stretching, the speed difference of a roll is not in inverse proportion to the thickness of a stretched film.

(Production Example A-1-2)
A PET resin having an intrinsic viscosity (IV) = 0.67 is extruded at 290 ° C. with a coat hanger type die head attached to a uniaxial melt extruder, and solidified on a casting drum cooled to 58 ° C. A 5 mm polymer film was obtained.
This polymer film was heated to 60 ° C. with a far-infrared heater, and uniaxial necking stretching (stretching speed: 6,000 mm / min) was performed 5.5 times.
Thus, the crystalline polymer film of Production Example A-1-2 was produced. The crystalline polymer film had a thickness of 100 μm, had a cavity, and exhibited a metallic luster. The film had no voids at a depth of 4 μm to 10 μm from the film surface, and the porosity was 19%.

(Comparative Production Example A-1)
PET (polyethylene terephthalate 100% resin) with intrinsic viscosity (IV) = 0.68 is extruded at 295 ° C. with a coat hanger type die head attached to a screw-type melt extruder, on a casting drum cooled to 60 ° C. Solidified to obtain a polymer film having a thickness of 0.5 mm.
This polymer film was uniaxially stretched (longitudinal stretching). Specifically, stretching (uniaxial) was performed at a speed of 500 mm / min in a heated atmosphere of 110 ° C.
The polymer molded body (polymer film) was stretched 4.2 times by the one-stage uniaxial stretching.
Thus, a crystalline polymer film of Comparative Production Example A-1 was produced. The crystalline polymer film had a thickness of 120 μm, had no voids, and did not exhibit a metallic luster.

Table 1 shows the composition of the films of Production Examples A-1-1 to A-1-2 and Comparative Production Example A-1.

(Evaluation A-1)
The films obtained in Production Examples A-1-1 to A-1-2 and Comparative Production Example A-1 were evaluated as follows.

(1) Measurement of thickness It measured using the Keyence Corporation make and long range contact-type displacement meter AF030 (measurement part), AF350 (indication part). The results are shown in Table 2.

(2) Measurement of light shielding rate (light shielding property)
Measurement was performed using a spectrophotometer U-4100 manufactured by Hitachi, Ltd. Light with a wavelength of 550 nm is incident perpendicularly on the surfaces of the films of the production examples A-1-1 to A-1-2 and the comparative production example A-1, and the production examples A-1-1 to A-1- 2 and the intensity of light transmitted through the film (sample) of Comparative Production Example A-1, and a blank without the films of Production Examples A-1-1 to A-1-2 and Comparative Production Example A-1 The light intensity was compared with the following evaluation criteria. The results are shown in Table 4.
Light blocking ratio (%) = 100-[{(light intensity of sample) / (intensity of blank light)} × 100]
A: The light shielding rate at a wavelength of 550 nm is 80% or more.
X: The light shielding rate at a wavelength of 550 nm is less than 80%.

(3) Measurement of the distance from the cavity located closest to the film surface to the film surface, perpendicular to the film surfaces of Production Examples A-1-1 to A-1-2 and Comparative Production Example A-1-1 In addition, a cross section perpendicular to the longitudinal stretching direction (see FIG. 4D) was examined using a scanning electron microscope at an appropriate magnification of 300 to 3,000 times, and a cross-sectional photograph was taken.
At the time of imaging, the films of Production Examples A-1-1 to A-1-2 and Comparative Production Example A-1 were set on a scanning electron microscope in a state where the films were placed in a plane, and the images were taken.
In the cross-sectional photograph, an arithmetic average value T of thickness was calculated. The arithmetic average value T of the thicknesses calculated for the films of each of Production Examples A-1-1 to A-1-2 and Comparative Production Example A-1 was measured in the above “(1) Measurement of thickness”. It was the same as the thickness (see Table 2).
Next, an arbitrary straight line parallel to the thickness direction was drawn in the cross-sectional photograph, and another straight line parallel to the single straight line and separated by 20 × T was drawn. Moreover, it confirmed that the cavity was orientating along the vertical extending | stretching direction by the examination by the said scanning electron microscope.
Then, in each cavity in the cross-sectional photograph, the center of the circle that minimizes the sum of squares of deviations from the reference circle arbitrarily set by the maximum square center method was determined, and this was set as the center of the cavity.
Then, in the region sandwiched between the one straight line and the other straight line, ten cavities having the shortest distance from the center of the cavity to the top surface of the film were selected. Note that the “distance from the center of the cavity to the top surface of the film” means that when drawing a circle centered on the “center of the cavity”, the radius of the circle to be drawn is sequentially increased, and an arc is the film first. The radius of the circle when touching the surface of.
Then, for the 10 selected cavities, a distance h (i) from each center to the upper surface of the film is calculated, and an arithmetic average value h (avg) of each calculated distance h (i) is expressed as (3 ). The results are shown in Table 2.
h (avg) = (Σh (i)) / 10 (3)

Table 2 shows the appearance, thickness, and h (ave) of the film.

(Production Example A-2-1: Molding of preform using PET resin)
A preform was injection molded using Unitika PET pellets (NEH2070).
The injection temperature was 295 ° C.-295 ° C.-260 ° C.-120 ° C.-40 ° C. in order from the nozzle tip, the injection pressure was 2,000 MPa, and the mold temperature was 15 ° C.
Thus, a preform of Production Example A-2-1 was obtained.

(Production Example A-2-2)
A preform was produced in the same manner as in Production Example A-2-1 except that the volume was optimized to be applied to the shapes of Examples A-4 and A-5 described later. It was.

Example A-1
Using the crystalline polymer film of Production Example A-1-2 and the preform of Production Example A-2-1, Container A-1 was produced as follows.

A predetermined printing was applied to the crystalline polymer film of Production Example A-1-2 (printed with the design of FIG. 13 using a pigment inkjet printer PX-9500S manufactured by EPSON), and then on the inner wall of the blow mold Along with it, it was cut into a fan shape so that it could be mounted without being overlapped or bent, and an adhesive was applied to make an insert film. As the adhesive, an ethylene-ethyl acrylate copolymer adhesive was used.

The crystalline polymer film was attached to the jig shown in FIG. 8B and sucked in the direction of the arrow, thereby bringing the crystalline polymer film into close contact with the jig.
A jig having the crystalline polymer film adhered thereto was inserted into the mold from under the blow mold (closed).
Then, after sucking the crystalline polymer film from the air suction slit of the blow mold, suction of the jig was stopped, and the jig was removed from the blow mold.
As described above, the crystalline polymer film was placed in the blow mold.

The preform heated in advance in Production Example A-2-1 was set in a blow mold on which the crystalline polymer film was placed, with the convex part of the base (reference numeral 56 in FIG. 7) fitted.
The preform was heated by an infrared panel heater until the body of the preform reached 90 ° C.

Next, simultaneously with the introduction of high-pressure air (pressure: 2 MPa, temperature: 100 ° C.), the stretching rod is formed from the surface of the base of the blow mold by the hydraulic cylinder, and the ceiling of the blow mold (the bottom of the blow molded body is formed). It was lifted at a speed of 10 cm / 0.5 sec up to 80% of the distance to (part).
As described above, the crystalline polymer film and the container having the inner diameter of the opening of 75 mm, the height of 115 mm, the outer diameter of the bottom surface of 62 mm, and the thickness of the body portion of 200 μm (the thickness of the crystalline polymer film is about 100 μm) To obtain a container A-1 (see FIG. 9).

In the container A-1, a crystalline polymer film was disposed on the entire body (side surface) of the container. At this time, the ratio (B / A) of the surface area (A) of the container A-1 to the area (B) of the crystalline polymer film in the container A-1 was 0.83 (83%).
Further, when the radius of curvature R of the corner portion of the side surface of the container A-1 was measured with a three-dimensional shape measuring apparatus, R = about 42 mm in the small R portion of the container bottom.

Example A-2
In Example A-1, the point where the crystalline polymer film was placed in the blow mold and the container was blow-molded was that the container was blow-molded without placing the crystalline polymer film in the blow mold, Thereafter, a container A-2 was produced in the same manner as in Example A-1, except that the crystalline polymer film was wound around the container.
The thickness of the body part of the blow molded container was 100 μm.
The crystalline polymer film is wound around the container with an adhesive having a width of 2 mm at the beginning and end of winding of the crystalline polymer film (both ends of the crystalline polymer film; part A in FIG. 10). It was performed by winding it around a container after coating and blow molding (see FIG. 10).

Example A-3
In Example A-2, the crystalline polymer film of Production Example A-1-1 was used as the crystalline polymer film. A container A-3 was produced in the same manner as in Example A-2, except that:

Example A-4
In Example A-1, the preform of Production Example A-2-1 was used as the preform in place of the preform of Production Example A-2-2. A container A-4 was produced in the same manner as in Example A-1, except for changing from to FIG. 11 below.
The container A-4 has an opening with a cross section of □ 70 mm, a height of 100 mm, a bottom cross section of □ 50 mm, and a body portion having a thickness of 500 μm (the thickness of the crystalline polymer film is about 120 μm) (FIG. 11). reference).
In the container A-4, a crystalline polymer film was disposed on the entire body (side surface) of the container. At this time, the ratio (B / A) of the surface area (A) of the container A-4 to the area (B) of the crystalline polymer film in the container A-4 was 0.30 (30%).
Further, when the radius of curvature R of the corner portion of the side surface of the container A-4 was measured with a three-dimensional shape measuring apparatus, R = 1 mm at a small portion of R at the bottom of the container.

Example A-5
In Example A-1, the preform of Production Example A-2-1 was used as the preform in place of the preform of Production Example A-2-2. To A in the same manner as in Example A-1, except for changing to FIG. 12 below.
The container A-5 has an opening with a section of 70 mm, a height of 120 mm, a bottom section of 40 mm, and a body thickness of 500 μm (the crystalline polymer film has a thickness of about 120 μm) (FIG. 12). reference).
In the container A-5, a crystalline polymer film was disposed on the entire body (side surface) of the container. At this time, the ratio (B / A) of the surface area (A) of the container A-5 to the area (B) of the crystalline polymer film in the container A-5 was 0.30 (30%).
Further, when the radius of curvature R of the corner portion of the side surface of the container A-5 was measured by a three-dimensional shape measuring apparatus, R = 0.8 mm at the small R portion of the container bottom.

(Comparative Example A-1)
A container A-6 was produced in the same manner as in Example A-2 except that the crystalline polymer film was not used in Example A-2.

(Comparative Example A-2)
In Example A-1, except that the crystalline polymer film of Production Example A-1-2 was used, except that the crystalline polymer film containing no cavity of Comparative Production Example A-1 was used. Container A-7 was produced in the same manner as Example A-1.

Table 3 summarizes the configurations of the containers of Examples A-1 to A-5 and Comparative Examples A-1 to A-2.

(Evaluation A-2)
The containers of Examples A-1 to A-5 and Comparative Examples A-1 to A-2 were evaluated as follows.

(1) Measurement of thermal insulation (heat retention) In a 25 ° C room, fill the container with 85 ° C warm water up to the upper brim, and put a thermometer on the outer surface of the container 1/3 height below the container. A thermocouple) was attached. And the temperature change of the thermometer was measured with time.
Table 4 shows the results of evaluation according to the following evaluation criteria based on the measurement results.
◯: The difference between the outer surface of the container after 3 minutes and the hot water temperature is 10 ° C. or more.
(Triangle | delta): The difference of the outer surface of a container and warm water temperature after 3 minutes is 5 degreeC or more and less than 10 degreeC.
X: The difference between the outer surface of the container after 3 minutes and the hot water temperature is less than 5 ° C.

(2) Strength measurement Set the digital force gauge DS-2 type (manufactured by Imada Co., Ltd.) with the attached flat attachment attached to the container on the compression manual measurement stand SV-1 (manufactured by Imada Co., Ltd.). The value of the digital force gauge was measured when the measuring unit was pressed against a predetermined position on the side surface of the container and pressed (deformed) by 3 mm. It shows that intensity | strength is excellent, so that the value of this digital force gauge is large.
The predetermined position (measurement position) of the side surface was set to a position that was a half of the distance from the opening (top) to the bottom of the container.
Table 4 shows the results of evaluation according to the following evaluation criteria based on the above results.
A: 5N or more: Can be held normally without problems.
◯: 3N or more and less than 5N.
Δ: Greater than 1.5N and less than 3N. It can be held somehow, but considerable care must be taken for holding. Difficult to hold in children.
X: 1.5N or less: The container is very fragile and easily crushed when held by hand and cannot be used.

(3) Presence / absence of cavities in the crystalline polymer film at the corners on the side of the container A sample was largely cut out, embedded in a resin, and cut with a microtome to obtain a cross-sectional sample. Next, the cross section was observed with a scanning electron microscope, and the presence or absence of a cavity of the crystalline polymer film at the corner of the side surface of the container was examined.
Table 4 shows the results of evaluation according to the following evaluation criteria based on the above results.
○: The thickness of the cavity portion measured from the electron microscope cross-sectional photograph of the film after being wound around the container is 80% with respect to the thickness of the cavity portion measured from the electron microscope cross-sectional photograph of the film before being wound around the container. more than.
Δ: The thickness of the cavity portion measured from the electron microscope cross-sectional photograph of the film after being wound around the container is 50% of the thickness of the cavity portion measured from the electron microscope cross-sectional photograph of the film before being wound around the container. Greater than 80%.
X: The thickness of the cavity part measured from the electron microscope cross-sectional photograph of the film after being wound around the container is 50% with respect to the thickness of the cavity part measured from the electron microscope sectional photograph of the film before being wound around the container. Less than (the cavity has been crushed).

(4) Comprehensive evaluation Table 4 shows the results of comprehensive evaluation with the following evaluation criteria.
◯: None of the evaluation items (light shielding properties, heat insulating properties, strength, cavities at the corners) have x or Δ.
Δ: There is at least one Δ in each of the evaluation items (light shielding properties, heat insulating properties, strength, and cavities at corners).
X: There is at least one x in each of the evaluation items (light-shielding property, heat insulating property, strength, cavity at the corner).

From the results shown in Table 4, the containers A-1 to A-5 of Examples A-1 to A-5 wound with the crystalline polymer film containing the cavities inside are highly crystalline. It was found that the container is comprehensively superior compared to the containers A-6 to A-7 of Comparative Examples A-1 to A-2 in which no molecular film is wound.
It was also found that Example A-1 in which the crystalline polymer film and the container were integrated had superior strength compared to Examples A-2 to A-3 that were not integrated.
Further, in the containers A-1 to A-4 of Examples A-1 to A-4 in which the corner portion R on the side surface of the container is 1 mm or more, the corner cavity is particularly retained.
Among Examples A-1, A-4, and A-5 in which the crystalline polymer film and the container are integrated, Example A-1 having a high ratio ((B / A) × 100) is particularly preferable. I found it excellent.
From the above results, the containers of Examples A-1 to A-5, which are the containers of the present invention, are excellent in strength, light-shielding properties, and heat-retaining properties, and can be easily compressed to reduce the volume and recycled. It was found that it was excellent in design and design.

(Production Example B-1)
PBT (polybutylene terephthalate 100% resin) with IV = 0.72 was extruded from a T-die at 248 ° C. using a melt extruder and solidified with a casting drum, and a polymer molded body (polymer film) having a thickness of about 265 μm Got. This polymer molded body (polymer film) was uniaxially stretched (longitudinal stretching).
Specifically, uniaxial stretching was performed at a speed of 120 mm / min in an atmosphere of 42 ° C., and after confirming that necking had occurred, a further uniaxial movement was performed in the same direction as the beginning at a speed of 6,000 mm / min. Stretched.
The polymer molded body (polymer film) was stretched 4.5 times by the two-stage uniaxial stretching.
Thus, the crystalline polymer film of Production Example B-1 was produced.

(Production Example B-2)
PHT (polyhexamethylene terephthalate 100% resin) with IV = 0.70 was extruded from a T-die at 180 ° C. using a melt extruder and solidified with a casting drum to give a polymer molded body (polymer film) having a thickness of about 276 μm. ) This polymer molded body (polymer film) was uniaxially stretched (longitudinal stretching).
Specifically, in an atmosphere of 22 ° C., uniaxially stretching at a speed of 100 mm / min and confirming that necking has occurred, and then further uniaxially in the same direction as the beginning at a speed of 5,200 mm / min. Stretched.
The polymer molded body (polymer film) was stretched 4.8 times by the two-stage uniaxial stretching.
Thus, a crystalline polymer film of Production Example B-2 was produced.

(Production Example B-3)
PBS (polybutylene succinate 100% resin) with IV = 0.67 was extruded from a T-die at 135 ° C. using a melt extruder and solidified with a casting drum to give a polymer molded body (polymer film) having a thickness of 281 μm. Got. This polymer molded body (polymer film) was uniaxially stretched (longitudinal stretching).
Specifically, in an atmosphere of 15 ° C., uniaxial stretching was performed at a speed of 100 mm / min, and after confirming that necking had occurred, the uniaxial stretching was further performed in the same direction as the beginning at a speed of 4,800 mm / min. Stretched.
The polymer molded body (polymer film) was stretched 5.5 times by the two-stage uniaxial stretching.
Thus, a crystalline polymer film of Production Example B-3 was produced.

(Production Example B-4)
Isotactic polypropylene (isoPP) (manufactured by Aldrich) having a weight average molecular weight of 190,000, a number average molecular weight of 50,000, Tg of -13 ° C., and a melting point of 170 ° C. to 175 ° C. at 210 ° C. using a melt extruder. And solidified with a casting drum to obtain a polymer molded body (polymer film) having a thickness of 363 μm. This polymer molded body (polymer film) was uniaxially stretched (longitudinal stretching).
Specifically, uniaxial stretching was performed at a speed of 100 mm / min in an atmosphere of 35 ° C., and after confirming that necking had occurred, a further uniaxial movement was performed in the same direction as the beginning at a speed of 11,000 mm / min. Stretched.
The polymer molded body (polymer film) was stretched 7.2 times by the two-stage uniaxial stretching.
Thus, a crystalline polymer film of Production Example B-4 was produced.

(Production Example B-5)
PBT (polybutylene terephthalate 100% resin, glass transition temperature (Tg) = 39 ° C.) with IV = 0.70 was extruded from a T die at 250 ° C. using a melt extruder and solidified with a casting drum to obtain a thickness. A polymer molded body (polymer film) of about 263 μm was obtained. This polymer molded body (polymer film) was uniaxially stretched (longitudinal stretching).
Specifically, uniaxial stretching was performed at a speed of 120 mm / min in an atmosphere of 58 ° C., and after confirming that necking had occurred, a further uniaxial movement was performed in the same direction as the beginning at a speed of 4,000 mm / min. Stretched.
The polymer molded body (polymer film) was stretched 4.5 times by the two-stage uniaxial stretching, and the lateral stretching was not performed.
Thus, the crystalline polymer film of Production Example B-5 was produced.

(Comparative Production Example B-1)
A 45 μm thick polyethylene terephthalate film (Toyobo Co., Ltd., S7561) was prepared as a heat-shrinkable synthetic resin film. On the heat-shrinkable synthetic resin film, gravure printing was performed using NT-Hilamic Indigo (manufactured by Dainichi Seika Co., Ltd.) as a pattern printing layer using a halftone plate having a plate depth of 28 μm and a line number of 175 lines. On the pattern printing layer, a white ink (entire solid printing) layer is NT-Hilamic Conk White (manufactured by Dainichi Seika Co., Ltd.), using a halftone plate with a plate depth of 28 μm and a line number of 175 lines. Gravure printing was performed by two overprints of solid printing. On top of the white ink (full solid printing) layer, as a white ink (full solid printing) layer containing aluminum paste, NT-Hilamic Conk White (manufactured by Dainichi Seika Co., Ltd., aluminum paste content: 1% by weight) ), A solid gravure printing was performed using a halftone plate having a plate depth of 28 μm and a line number of 175 lines. As a result, a film of Comparative Production Example B-1 comprising a polyethylene terephthalate film / pattern printing layer / white ink (whole surface printing twice) layer / white ink (aluminum paste content: 1% by weight) whole surface printing layer was obtained. It was.

(Comparative Production Example B-2)
<Preparation of UV-absorbing shrink film>
In a 300 ml separable flask equipped with a Dimroth, dropping funnel, thermometer, nitrogen inlet tube, and stirring device, 30.0 g of 2- [2′-hydroxy-5 ′-(methacryloyloxy) phenyl] benzotriazole, methyl methacrylate 50 g, 15 g of butyl acrylate, 2 g of methacrylic acid, 0.5 g of 2-hydroxyethyl methacrylate, 1.6 g of n-dodecyl mercaptan and 100 g of ethyl acetate were added, and the temperature was raised to 50 ° C. while blowing nitrogen from the nitrogen introduction tube. Thereafter, 0.3 g of azobisisobutyronitrile dissolved in a small amount of ethyl acetate was added dropwise over 30 minutes. After the completion of the addition, the temperature was raised to 70 ° C., and the reaction was carried out for 8 hours. A coalescence was prepared. The UV-absorbing acrylic copolymer was applied to a 50 μm-thick shrink polyethylene terephthalate (Ci Kasei Co., Ltd., bonset) to a dry film thickness of 5 μm, and then dried at 60 ° C. for 30 seconds. A UV-absorbing shrink film was prepared.

<Preparation of light-shielding pressure-sensitive adhesive>
To a 300 ml separable flask equipped with a Dimroth, dropping funnel, thermometer, nitrogen inlet tube, and stirrer were added 55 g of 2-ethylhexyl acrylate, 25 g of vinyl acetate, 4 g of 2-hydroxyethyl methacrylate, and 100 g of ethyl acetate, and a nitrogen inlet tube Then, the temperature was raised to 50 ° C. while blowing nitrogen. Thereafter, 0.3 g of azobisisobutyronitrile dissolved in a small amount of ethyl acetate was added dropwise over 30 minutes, and after completion of the addition, the temperature was raised to 70 ° C., and the reaction was carried out for 8 hours. A solution was prepared.
1 part by weight of titanium oxide having an average particle size of 0.03 μm was blended with 100 parts by weight of the adhesive acrylic copolymer solution, and was dispersed for 1 hour by a three-roll mill. After dispersion, 0.13 parts by weight of Coronate L (manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanate-based crosslinking agent) was blended to prepare a light-shielding pressure-sensitive adhesive.

<Preparation of film>
The light-shielding pressure-sensitive adhesive prepared in the preparation of the light-shielding pressure-sensitive adhesive is applied to release paper (SP-8E, manufactured by Lintec Corporation) with an applicator so as to have a dry film thickness of 25 μm, and is circulated with hot air at 100 ° C. Machine dried for 2 minutes. After drying, the film was affixed to the ultraviolet-absorbing shrink film prepared in the preparation of the ultraviolet-absorbing shrink film to prepare a film of Comparative Production Example B-2.

Table 5 summarizes the film configurations and the like of Production Examples B-1 to B-5 and Comparative Production Examples B-1 to B-2.

(Evaluation B-1)
The films of Production Examples B-1 to B-5 and Comparative Production Examples B-1 to B-2 were evaluated as follows.

(1) Measurement of thickness The thickness was measured in the same manner as (1) Measurement of thickness in Evaluation A-1.

(2) Measurement of light transmittance (light shielding property)
The transmittance was measured using a spectrophotometer (U-4100, manufactured by Hitachi, Ltd.). Light was incident from the normal direction of the surface of the obtained film (sample), and the intensity of light transmitted through the film was compared with the value of a blank that did not transmit the film. The transmittance (%) was measured using a wavelength of 400 nm.
Light transmittance (%) = {(sample light intensity) / (blank light intensity)} × 100
Table 8 shows the results of evaluation based on the following evaluation criteria.
A: 10% or less.
○: Greater than 10% and 20% or less.
Δ: Greater than 20% and 30% or less.
X: Greater than 30%.

(3) Measurement of heat shrinkage rate The films of Production Examples B-1 to B-5 and Comparative Production Examples B-1 to B-2 were cut into 100 mm squares, and the samples were adjusted to 150 ° C. After heat treatment for 10 minutes in the oven, the dimensions of the film stretching direction (first direction) and the direction perpendicular to the film stretching direction (first direction) (second direction) are measured, and the respective heat The shrinkage was determined according to the following formula. However, the oven temperature was changed to 100 ° C. for the measurement of the heat shrinkage rate of the film of Production Example B-3.

(4) Measurement of the distance from the cavity closest to the film surface to the film surface As in (3) Measurement of the distance from the cavity closest to the film surface to the film surface in Evaluation A-1 It was measured.
It should be noted that the arithmetic average value T of the thicknesses calculated in the films of each of the above Production Examples B-1 to B-5 and Comparative Production Examples B-1 to B-2 is “(1) Thickness” in the evaluation B-1. It was the same as the thickness (see Table 6) measured in “Measurement of”.

(5) Measurement of heat insulation (heat retention) The films of the above Production Examples B-1 to B-5 and Comparative Production Examples B-1 to B-2 (reference numeral 62 in FIG. 14A) were made of aluminum bottles (350 mL containers, A thin temperature sensor (reference numeral 63 in FIG. 14A) having a diameter of about 0.5 mm is attached to the side surface of reference numeral 61) in FIG. 14A, and a PET adhesive film (10 mm × 10 mm, thickness 10 μm, Affixing was performed using reference numeral 64) in FIG. 14A. The temperature sensor was also attached to the opposite side of the bottle at 180 ° in the same manner, and was attached to a total of two places (reference numerals 63 (1) and 63 (2) in FIG. 14B) (see FIGS. 14A to 14B, FIG. 14A is a view of the bottle as seen from the front, and FIG. 14B is a view of the bottle as seen from above.
Water was put into this bottle, and it was put into a minus 20 ° C. freezer for 10 hours to freeze the water. At this time, the bottle lid was not capped to prevent the bottle from bursting.
The bottle was taken out into a room at 25 ° C., and the temperature sensor part was held with a finger (one temperature sensor with the thumb and the other temperature sensor with the middle finger) to lift the container (see FIG. 14C). .
At this time, the heat insulation was evaluated according to the following evaluation criteria. The results are shown in Table 6.
○: The temperature sensor showed 5 ° C. or higher, and the bottle could be held for 5 minutes.
X: The temperature sensor showed below 0 degree | times, and the fingertip holding the bottle became painful because of low temperature, and the bottle could not be held for 2 minutes or more.

The above evaluation results are summarized in Table 6.

Example B-1
<Winding process>
As the container, a PET bottle shown in FIG. 15 (the thickness of the straight body portion from XY to about 160 μm) was produced by injection molding and used.
The crystalline polymer film obtained in Production Example B-1 was wound around the container once.

<Shrink process>
By releasing the humidified steam at 105 ° C. from the nozzle to the atmosphere, it was sprayed onto the wound container with hot water to shrink the crystalline polymer film to obtain a container B-1.

The thickness of the crystalline polymer film in the container B-1 is 66 μm × 1 turn, and the surface area (A) of the container B-1 and the area (B) of the crystalline polymer film in the container B-1 Ratio ((B / A) × 100) to 75%.
In addition, the crystalline polymer film in the container B-1 was placed on the side surface.

(Examples B-2 to B-5, Comparative Examples B-1 to B-2)
In Example B-1, the points using the crystalline polymer film obtained in Production Example B-1 were obtained in Production Examples B-2 to B-5 and Comparative Production Examples B-1 to B-2. Containers of Examples B-2 to B-5 and Comparative Examples B-1 to B-2 were produced in the same manner as Example B-1, except that the obtained film was replaced.

(Example B-6)
In Example B-1, the ratio of the surface area (A) of the container to the area (B) of the crystalline polymer film in the container ((B / A) × 100) was set to 75%. A container of Example B-6 was produced in the same manner as Example B-1, except that the changes were made.

(Example B-7)
In Example B-1, the ratio of the surface area (A) of the container to the area (B) of the crystalline polymer film in the container ((B / A) × 100) was set to 75%. A container of Example B-7 was produced in the same manner as Example B-1, except that the changes were made.

Table 7 summarizes the configurations of the containers of Examples B-1 to B-7 and Comparative Examples B-1 to B-2.

(Evaluation B-2)
The containers of Examples B-1 to B-7 and Comparative Examples B-1 to B-2 were evaluated as follows.

(1) Measurement of strength The strength was measured and evaluated in the same manner as (2) Measurement of strength in Evaluation A-2.
Table 8 shows the evaluation results.

(Comprehensive evaluation)
Table 8 shows the results of comprehensive evaluation based on the following evaluation criteria based on the evaluation results of light shielding properties, heat insulating properties, and strength.
○: There is no x or Δ in each evaluation item.
Δ: Each evaluation item has at least one Δ.
X: There is at least one x in each evaluation item.

From the above results, the containers of Examples B-1 to B-7, which are the containers of the present invention, are excellent in strength, light-shielding property, and heat retention, and can be easily compressed to reduce the volume, and can be recycled. It was found to be excellent in performance.

The container of the present invention is excellent in strength, light-shielding property, and heat retaining property, and can be easily compressed to reduce the volume, is excellent in recyclability, and is also excellent in design properties. Can be suitably used.

DESCRIPTION OF SYMBOLS 1 Crystalline polymer film 1a Surface 11 Raw material 12 Extruder 13 T die 14 Casting roll 15 Longitudinal stretcher 15a Roll 16 Lateral stretcher 16a Clip 100 Cavity F Film or sheet L The length of the cavity in the orientation direction of the cavity r The cavity Length of cavity in thickness direction orthogonal to orientation direction 41 Crystalline polymer film 42 Jig 43 Blow mold 44 Slit 45 Suction nozzle 46 Suction hole 51 Blow mold (1)
52 Blow mold (2)
53 Crystalline polymer film 54 Stretched rod head 55 Preform 56 Base 57 Guide 58 Stretched rod 59 Air flow path 61 Bottle 62 Film 63 Temperature sensor 63 (1) Temperature sensor 63 (2) Temperature sensor 64 PET adhesive film

Claims

A container formed by winding a crystalline polymer film containing a crystalline polymer film containing therein a long cavity in a state in which the length direction is oriented in the first direction,
In the cross section perpendicular to the orientation direction of the cavities in the crystalline polymer film, the ten cavities having the shortest distance from the center of the cavities to the surface of the crystalline polymer film are the crystal from each center. The distance h (i) to the surface of the conductive polymer film is calculated, and the arithmetic average value h (avg) of each calculated distance h (i) satisfies the relationship of the following formula (1): Container to be used.
h (avg)> T / 100 (1)
However, in said Formula (1), T represents the arithmetic mean value of the thickness in the said cross section, and the ten said cavities are parallel to the arbitrary 1 straight line parallel to the said thickness direction, and the said 1 straight line. And a cavity existing in a region sandwiched by other straight lines located 20 × T apart.
The container according to claim 1, wherein a radius of curvature R of a corner portion on the side surface of the container is 1 mm or more.
The container according to claim 1, wherein the crystalline polymer film in the container has a thickness of 30 μm or more and 500 μm or less.
The ratio ((B / A) x 100) of the surface area (A) of the container and the area (B) of the crystalline polymer film in the container is 25% or more. container.
The container according to any one of claims 1 to 4, wherein the crystalline polymer film and the container are integrated.
The container according to claim 1, wherein the crystalline polymer film wound around the container is contracted.
The container according to claim 6, wherein the heat shrinkage rate of the crystalline polymer film at 150 ° C is 10% or more in the first direction and 5% or less in the second direction orthogonal to the first direction.
The container according to claim 6, wherein the thickness of the crystalline polymer film in the container is 45 μm or more and 300 μm or less.
9. The ratio ((B / A) × 100) between the surface area (A) of the container and the area (B) of the crystalline polymer film in the container is 30% or more. 9. container.
10. The container according to claim 6, wherein the transmittance of the crystalline polymer film with respect to light having one wavelength selected from wavelengths of 300 nm to 780 nm is 10% or less.
A step of disposing a crystalline polymer film containing a crystalline polymer and containing a long cavity inside the blow mold in a state where the length direction is oriented in the first direction;
Placing a preform in a blow mold in which the crystalline polymer film is placed;
Blowing the preform,
In the cross section perpendicular to the orientation direction of the cavities in the crystalline polymer film, the ten cavities having the shortest distance from the center of the cavities to the surface of the crystalline polymer film are the crystal from each center. The distance h (i) to the surface of the conductive polymer film is calculated, and the arithmetic average value h (avg) of each calculated distance h (i) satisfies the relationship of the following formula (1): A method for manufacturing a container.
h (avg)> T / 100 (1)
However, in said Formula (1), T represents the arithmetic mean value of the thickness in the said cross section, and the ten said cavities are parallel to the arbitrary 1 straight line parallel to the said thickness direction, and the said 1 straight line. And a cavity existing in a region sandwiched by other straight lines located 20 × T apart.
A step of winding a crystalline polymer film comprising a polymer having crystallinity and containing a long cavity inside thereof in a state in which the length direction is oriented in the first direction;
Shrinking the wound crystalline polymer film,
In the cross section perpendicular to the orientation direction of the cavities in the crystalline polymer film, the ten cavities having the shortest distance from the center of the cavities to the surface of the crystalline polymer film are the crystal from each center. The distance h (i) to the surface of the conductive polymer film is calculated, and the arithmetic average value h (avg) of each calculated distance h (i) satisfies the relationship of the following formula (1): A method for manufacturing a container.
h (avg)> T / 100 (1)
However, in said Formula (1), T represents the arithmetic mean value of the thickness in the said cross section, and the ten said cavities are parallel to the arbitrary 1 straight line parallel to the said thickness direction, and the said 1 straight line. And a cavity existing in a region sandwiched by other straight lines located 20 × T apart.