JP2021123705A - Resin film, method for producing the same, and molding - Google Patents

Abstract

To provide a resin film that is formed from a poly(3-hydroxy butyrate) resin, is a long, thin and wide film but has high thickness accuracy in width direction, and a method for producing the resin film.SOLUTION: A resin film comprises a poly(3-hydroxy butyrate) resin, has a width of 500 mm or more, a length of 100 m or more, and a thickness of 20-500 μm, and has a thickness accuracy (±μm)×A of 8 or less in width direction, where, A is a value calculated by formula: (1+(200-thickness (μm))×0.002).SELECTED DRAWING: Figure 1

Description

The present invention relates to a resin film composed of a poly (3-hydroxybutyrate) resin, a method for producing the same, and a molded product on which the resin film is molded.

In recent years, separate collection and composting of kitchen waste have been promoted mainly in Europe, and plastic products that can be composted together with kitchen waste are desired. As an example of such a plastic product, Patent Document 1 discloses a processed product obtained by thermoforming a sheet made of a polylactic acid-based polymer.

On the other hand, the environmental problems caused by waste plastics have been highlighted, and it has become clear that a large amount of plastics that have flowed into the sea via ocean dumping or rivers are drifting in the ocean on a global scale. Since such plastics maintain their shape for a long period of time, they have an impact on the ecosystem, such as so-called ghost fishing, which restrains and captures marine organisms, and when ingested by marine organisms, they stay in the digestive tract and cause feeding disorders. Has been pointed out.

Furthermore, it has been pointed out that microplastics, which are disintegrated and atomized by ultraviolet rays, adsorb harmful compounds in seawater, and when marine organisms ingest them, harmful substances are taken into the food chain. There is.

The use of biodegradable plastics is expected for marine pollution caused by such plastics, but according to a report compiled by the United Nations Environmental Plan in 2015, the temperature of plastics that can be biodegradable with compost such as polylactic acid is high. It has been pointed out that it cannot be a countermeasure for marine pollution because it cannot be expected to decompose in a short period of time in the low actual ocean.

Under these circumstances, poly (3-hydroxybutyrate) resin is a material that can undergo biodegradation even in seawater, and is therefore attracting attention as a material that solves the above problems.

Patent Document 2 describes a polyester resin composition containing two types of polyhydroxyalkanoates, and an example of a molded product thereof is a film or sheet (paragraph [0067]), and has a width of 100 mm and a thickness of 100 mm. It is stated that a 100 μm sheet was produced (paragraph [0119]).

JP-A-2002-248677 International Publication No. 2015/146194

Poly (3-hydroxybutyrate) resin generally has a low thermal decomposition temperature and has a property of being difficult to crystallize. Therefore, it is difficult to industrially produce a film using a poly (3-hydroxybutyrate) resin. In particular, a resin film that is long, thin, and wide, but has high film thickness accuracy in the width direction is made of poly. It was difficult to produce from a (3-hydroxybutyrate) resin. Also in Patent Document 2, the production of a sufficiently wide resin film has not been studied.

In view of the above situation, it is an object of the present invention to provide a long, thin, wide resin film having high film thickness accuracy in the width direction by using a poly (3-hydroxybutyrate) resin. And.

The present invention is composed of a poly (3-hydroxybutyrate) resin, has a width of 500 mm or more, a length of 100 m or more, a film thickness of 20 to 500 μm, and a film thickness accuracy (± μm) × A in the width direction. The present invention relates to a resin film having a value of 8 or less. However, A is a numerical value calculated from the formula: (1+ (200-film thickness (μm)) × 0.002).
Preferably, the resin film is rolled into a roll.
Preferably, the resin film has a total haze (%) / film thickness (μm) ratio of less than 0.3.
Preferably, the poly (3-hydroxybutyrate) resin contains poly (3-hydroxybutyrate-co-3-hydroxyhexanoate).
The present invention is a method for producing the resin film.
A step of melting the poly (3-hydroxybutyrate) resin in an extruder and continuously extruding a film-like molten resin from a T-die, and
The process includes a step of transporting the film-shaped molten resin while bringing one side of the film-shaped molten resin into contact with a cooling roll or an endless belt arranged under the T-die.
The set temperature of the cooling roll or the endless belt is 40 to 60 ° C.
It also relates to a manufacturing method in which the contact time between the film-shaped molten resin and the cooling roll or endless belt is 2.2 seconds or more.
Further, the present invention relates to a molded product formed by cutting out the resin film as necessary and subjecting it to thermoforming.
Preferably, at least a part of the molded product is given a three-dimensional shape.

According to the present invention, it is possible to provide a long, thin, wide resin film having high film thickness accuracy in the width direction by using a poly (3-hydroxybutyrate) resin. Although the resin film of the present invention is a thin film, it has good moldability when the resin film is thermoformed. Further, the resin film may be wound in a roll shape, and since the film thickness accuracy is high, the appearance of the roll can be improved. Further, according to the production method of the present invention, from a poly (3-hydroxybutyrate) resin, a long and thin resin film having a wide film thickness in the width direction and a good appearance can be obtained. Can be manufactured.

The schematic diagram explaining the manufacturing method which concerns on one Embodiment of this invention. Schematic diagram for explaining the manufacturing method of the comparative example in which the sandwiching roll is arranged directly under the T-die.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

The poly (3-hydroxybutyrate) -based resin in the present application is an aliphatic polyester resin that can be produced from microorganisms, and is a polyester resin having 3-hydroxybutyrate as a repeating unit. The poly (3-hydroxybutyrate) resin may be a poly (3-hydroxybutyrate) having only 3-hydroxybutyrate as a repeating unit, or 3-hydroxybutyrate and other hydroxyalkanoates. It may be a copolymer with. Further, the poly (3-hydroxybutyrate) resin may be a mixture of a homopolymer and one or more copolymers, or a mixture of two or more copolymers.

Specific examples of the poly (3-hydroxybutyrate) -based resin include poly (3-hydroxybutyrate), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate), and poly (3-hydroxybutyrate). Rate-co-3-hydroxyvariate), poly (3-hydroxybutyrate-co-4-hydroxybutyrate), poly (3-hydroxybutyrate-co-3-hydroxyoctanoate), poly (3-hydroxybutyrate), poly (3-hydroxybutyrate) Hydroxybutyrate-co-3-hydroxyoctadecanoate) and the like. Among them, poly (3-hydroxybutyrate), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate), and poly (3-hydroxybutyrate-co-) are easy to produce industrially. 3-Hydroxyvariate) and poly (3-hydroxybutyrate-co-4-hydroxybutyrate) are preferred.

Furthermore, by changing the composition ratio of the repeating unit, the melting point and crystallinity can be changed, and the physical properties such as Young's modulus and heat resistance can be changed, and the physical properties between polypropylene and polyethylene can be imparted. Poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) is preferable from the viewpoint of being possible, industrially easy to produce as described above, and being a physically useful plastic. .. In particular, among poly (3-hydroxybutyrate) -based resins having the property of being easily thermally decomposed under heating at 180 ° C. or higher, poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) has a low melting point. It is also preferable from the viewpoint that it can be molded at a low temperature.

The composition ratio of the repeating unit of the poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) is the 3-hydroxybutyrate unit / 3-hydroxyhexanoate unit from the viewpoint of the balance between flexibility and strength. The composition ratio of is preferably 80/20 to 99/1 (mol / mol), and more preferably 75/15 to 97/3 (mo1 / mo1). The reason is that 99/1 or less is preferable from the viewpoint of flexibility, and 80/20 or more is preferable from the viewpoint that the resin has an appropriate hardness.

Examples of commercially available products of poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) include Kaneka Corporation "Kaneka Biodegradable Polymer PHBH" (registered trademark).

The melting point, Young's modulus, etc. of the poly (3-hydroxybutyrate-co-3-hydroxyvalerate) change depending on the ratio of the 3-hydroxybutyrate component and the 3-hydroxyvalerate component, but both components are co-crystallized. The crystallinity is as high as 50% or more due to crystallization, and although it is more flexible than poly (3-hydroxybutyrate), the improvement of brittleness is insufficient.

The resin film may contain a resin other than the poly (3-hydroxybutyrate) resin as long as the effects of the invention are not impaired. Examples of such other resins include aliphatic polyester resins such as polybutylene succinate adipate, polybutylene succinate, polycaprolactone, and polylactic acid, polybutylene adipate terephthalate, polybutylene succinate terephthalate, and polybutylene aze. Examples thereof include aliphatic aromatic polyester-based resins such as rate terephthalate. As the other resin, only one kind may be contained, or two or more kinds may be contained.

The content of the other resin is not particularly limited, but is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the poly (3-hydroxybutyrate) resin. The lower limit of the content of the other resin is not particularly limited and may be 0 parts by weight.

Further, the resin film may contain an additive that can be used together with the poly (3-hydroxybutyrate) resin as long as the effect of the invention is not impaired. Such additives include inorganic fillers such as talc, calcium carbonate, mica and silica, colorants such as pigments and dyes, odor absorbers such as activated charcoal and zeolite, fragrances such as vanillin and dextrin, plasticizers and oxidation. Examples thereof include inhibitor, antioxidant, weather resistance improving agent, ultraviolet absorber, crystal nucleating agent, lubricant, mold release agent, water repellent, antibacterial agent, slidability improving agent and the like. As the additive, only one kind may be contained, or two or more kinds may be contained. The content of these additives can be appropriately set by those skilled in the art according to the purpose of use.

The resin film is long and wide. Specifically, the length of the resin film is preferably 100 m or more, more preferably 200 m or more, further preferably 300 m or more, and particularly preferably 400 m or more. The upper limit is not particularly limited, but for example, 5000 m or less is preferable, and 3000 m or less is more preferable.

The width of the resin film is preferably 500 mm or more, more preferably 700 mm or more, further preferably 900 mm or more, and particularly preferably 1000 mm or more. The upper limit is not particularly limited, but for example, 5000 mm or less is preferable, and 3000 mm or less is more preferable.

The film thickness of the resin film is preferably 20 to 500 μm. If the thickness of the resin film is thinner than the above range, it becomes difficult to manufacture the resin film, and conversely, if the thickness of the resin film is thicker, the resin film is thermoformed to have a relatively uniform wall thickness and a good appearance. It becomes difficult to obtain a good molded product. The film thickness of the resin film is more preferably 30 to 400 μm, further preferably 40 to 350 μm, and particularly preferably 50 to 300 μm.

Although the resin film is wide as described above, the film thickness accuracy in the width direction is high. Specifically, the film thickness accuracy (± μm) × A in the width direction is 8 or less. .. However, since the absolute value of the film thickness accuracy can be affected by the magnitude of the film thickness, A is a parameter for alleviating the influence, and the formula: (1+ (200-film thickness (μm)) × 0.002. ) Is a numerical value calculated from. The film thickness accuracy (± μm) × A in the width direction is preferably 5 or less, more preferably 4 or less, and further preferably 3 or less. As described above, since the resin film has high film thickness accuracy, the moldability when the resin film is subjected to thermoforming is good, and a molded product having a good appearance can be obtained by thermoforming, and the resin. When the film is rolled into a roll, the outer surface of the roll has less unevenness, and the appearance of the roll can be improved.

The resin film can be highly transparent. Specifically, the ratio of the total haze (%) of the resin film to the film thickness (μm) of the resin film is preferably less than 0.3, more preferably 0.25 or less, and further preferably 0. .2 or less.

Next, an embodiment of the method for producing the resin film will be described with reference to FIG.
First, the film raw material containing the poly (3-hydroxybutyrate) resin is melted in an extruder. The T-die (11) is connected downward to the outlet of the extruder, and the film-like molten resin (12) is continuously extruded downward from the T-die (11). A cooling roll (13) is arranged directly below the T-die (11), and the extruded film-like molten resin (12) is conveyed while one side of the extruded film-like molten resin (12) is in contact with the cooling roll (13). .. When the molten resin (12) comes into contact with the cooling roll (13), crystallization of the poly (3-hydroxybutyrate) resin proceeds, and the resin film can be converted into an unmelted resin film.

The cooling roll (13) is a cylindrical member configured so that the surface temperature can be set. An endless belt for cooling may be arranged instead of the cooling roll. The endless belt is also configured so that the surface temperature can be set.

Generally, a poly (3-hydroxybutyrate) resin has an extremely slow crystallization rate as compared with other crystalline resins such as polypropylene, which makes continuous production of a film difficult. By adopting the manufacturing conditions described in the above, continuous production of long, thin, wide resin films with high film thickness accuracy in the width direction from poly (3-hydroxybutyrate) resins can be achieved. It can be realized.

When the film-shaped molten resin is brought into contact with the cooling roll or the endless belt, it is sandwiched directly under the T-die (11) so as to face the cooling roll (13) or the endless belt as shown in FIG. It is preferable not to adopt the method of arranging the built-in roll (14) to pressurize the film from both sides. Since the poly (3-hydroxybutyrate) resin immediately after being extruded from the T-die has not sufficiently crystallized, when both sides of the film are pressed directly under the T-die, the film is thin and wide, but it is wide. It becomes difficult to manufacture a resin film having high film thickness accuracy in the width direction.

From the viewpoint of promoting crystallization of the poly (3-hydroxybutyrate) -based resin by contact with the cooling roll or endless belt and avoiding sticking to the cooling roll or endless belt, the cooling roll or The temperature of the endless belt is preferably set to 40 to 60 ° C. When the temperature is lower than 40 ° C. or higher than 60 ° C., the crystallization of the poly (3-hydroxybutyrate) resin does not proceed sufficiently in the continuous production of the resin film, so that the cooling roll or the endless belt When the film is to be peeled off from the film, the film sticks to the cooling roll or the endless belt, and a long, thin, wide resin film with high film thickness accuracy in the width direction is manufactured. It becomes difficult to do. The temperature is preferably 43 to 55 ° C, more preferably 45 to 50 ° C.

Further, in order to promote the crystallization of the poly (3-hydroxybutyrate) resin by the contact with the cooling roll or the endless belt, the contact time between the film-like molten resin and the cooling roll or the endless belt is set. It is preferably long, and specifically, the contact time is preferably 2.2 seconds or more. If the contact time is shorter than 2.2 seconds, the poly (3-hydroxybutyrate) resin is insufficiently crystallized, and when the film is to be peeled off from the cooling roll or the endless belt, the cooling is performed. The film sticks to the roll or the endless belt, which makes it difficult to produce a long, thin, wide resin film with high film thickness accuracy in the width direction. The upper limit of the contact time is not particularly limited, but from the viewpoint of productivity, for example, 20 seconds or less is preferable, and 10 seconds or less is more preferable.

The contact time is adjusted so that the extrusion speed from the T-die or the take-up speed of the film is adjusted, and the distance between the film-like molten resin and the cooling roll or the endless belt is increased. This can be achieved by adjusting the transport path, the diameter of the roll and the length of the endless belt.

The resin film can be used for molding into a molded product such as a container by thermoforming after cutting it into a desired size as needed. Thermoforming can be carried out by fixing the end of the film with a clamp or pin, preheating the film using a far-infrared heater or the like to soften it, and then placing the film along the mold in vacuum or compressed air. .. Specific examples of the thermoforming include vacuum molding, pressure molding, vacuum pressure molding, matched molding, plug-assist molding, TOM molding, etc., but since they are simple and the mold cost is low, they are inexpensive. Vacuum forming and pressure forming are preferable.

The device used for preheating the resin film to the above temperature is not particularly limited, and examples thereof include a far-infrared heater, a heat ray heater, and a hot air heater. Among these, it is easy to heat the resin film quickly and uniformly. Therefore, a far-infrared heater is preferable. When using a far-infrared heater, the temperature of the heater is generally set higher than the target resin film temperature, and the temperature of the resin film is controlled by the distance between the heater and the resin film and the preheating time. For example, a method of installing a far-infrared heater set at 300 to 350 ° C. at a distance of 10 to 50 cm from the resin film and heating for 5 to 30 seconds can be mentioned. Examples of the actual temperature of the resin film include a method of measuring with a non-contact thermometer using infrared rays, a method of attaching a thermolabel whose color changes depending on the temperature to the resin film, and a method of setting preheating conditions.

The molded product obtained by thermoforming the resin film is not particularly limited, and for example, a container or packaging material having a recess in the center, a container or packaging material having a partition, or a container or packaging having a folded portion around an opening. Materials, etc. can be mentioned.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

(Film formation)
The film-forming property of the film was evaluated according to the following four-step criteria.
A: No film sticking to the cast roll, and a roll-shaped film with a width of 500 mm or more, a length of 100 m or more, and a film thickness accuracy (± μm) x A of 8 or less can be obtained. However, it is possible to obtain a roll-shaped film with a width of 500 mm or more, a length of 100 m or more, and a film thickness accuracy (± μm) × A of 8 or less. C: No film sticking to the cast roll. However, it is not possible to obtain a roll-shaped film with a width of 500 mm or more, a length of 100 m or more, and a film thickness accuracy (± μm) × A of 8 or less. Roll-shaped film with 100 m or more and film thickness accuracy (± μm) × A of 8 or less cannot be obtained.

(Film thickness accuracy)
The film thickness accuracy (± μm) in the width direction of the film was measured using a contact-type thickness measuring device (TOF-5R01, manufactured by Yamabun Electric Co., Ltd.). Moreover, the film thickness accuracy (± μm) × A was calculated. The A was calculated from the formula: (1+ (200-film thickness (μm)) × 0.002).

(Appearance of film)
The appearance of the film was visually confirmed and evaluated according to the following three criteria.
A: No cast roll peeling mark B: Some cast roll peeling marks C: Cannot be peeled from the cast roll

(Film haze)
The haze value of the film was measured according to JIS K 6174.

(Appearance of molded product)
A film piece having a size of 300 mm × 300 mm was cut out from the produced film, and the film piece was preheated so that the film temperature became 130 ° C., and thermoforming was performed. The moldability at that time was evaluated according to the following four-step criteria.
A: The molded body is shaped into a three-dimensional shape, and the molded body has no appearance defects such as wrinkles and surface roughness. B: The molded body is shaped into a three-dimensional shape, but the molded body has poor appearance such as wrinkles and surface roughness. There is C: There is a molding defect of the molded body D: The film is torn and molding is not possible

<Example 1>
45 parts by weight of poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (manufactured by Kaneka Corporation, Kaneka biodegradable polymer PHBH ^TM X131A) and 5 parts by weight of pentaerythritol were blended and dry blended. The obtained resin material is put into a φ26 mm isodirectional twin-screw extruder in which the cylinder temperature and the die temperature are set to 150 ° C., extruded, passed through a water tank filled with hot water at 45 ° C. to solidify the strands, and a pelletizer is used. By cutting, resin pellets X131N were obtained.
A raw material obtained by blending 50 parts by weight of the obtained X131N with 50 parts by weight of pelletized poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (Kaneka's biodegradable polymer PHBH ^TM X151C). Was melt-kneaded at a cylinder temperature of 155 ° C. using a φ90 mm diameter single-screw extruder with a T-die, discharged from the T-die at a die temperature of 170 ° C., and directly under the T-die without using a sandwiching roll. One side of the film-like resin was brought into contact with a cast roll adjusted to a temperature of 45 ° C. for 8.8 seconds and conveyed to obtain a film having a width of 1000 mm, a length of 400 m, and a thickness of 300 μm.

<Example 2>
The resin discharged from the T-die was brought into contact with the cast roll for 7.7 seconds and conveyed to obtain a film in the same manner as in Example 1 except that the thickness of the film was 200 μm.

<Example 3>
The resin discharged from the T-die was brought into contact with the cast roll for 2.2 seconds and conveyed to obtain a film in the same manner as in Example 1 except that the thickness of the film was 50 μm and the length was 500 m.

<Example 4>
The resin discharged from the T-die was brought into contact with the cast roll for 2.2 seconds and conveyed to obtain a film in the same manner as in Example 1 except that the thickness of the film was 20 μm and the length was 500 m.

<Example 5>
The resin discharged from the T-die was brought into contact with a cast roll whose temperature was adjusted to 55 ° C. for 2.2 seconds and conveyed, and the film was prepared in the same manner as in Example 1 except that the thickness of the film was 50 μm and the length was 500 m. Obtained.

<Comparative example 1>
Using a φ40 mm diameter single-screw extruder with a T-die, the cylinder temperature was melt-kneaded at 150 ° C, discharged from the T-die at a die temperature of 170 ° C, and the temperature was adjusted to 45 ° C directly under the T-die. The film-like resin was brought into contact with the cast roll for 10.6 seconds and conveyed while being sandwiched between the rubber rolls to obtain a film in the same manner as in Example 1 except that the film had a width of 300 mm, a length of 60 m, and a thickness of 200 μm. rice field. Since both sides of the film were pressed directly under the T-die while crystallization was not sufficiently progressed, the film thickness accuracy became 〇〇, and the film thickness accuracy deteriorated as compared with Examples 1 to 5.

<Comparative example 2>
An attempt was made to produce a film in the same manner as in Example 1 except that the resin discharged from the T-die was brought into contact with the cast roll for 2.0 seconds, but the contact time between the cast roll and the resin was short and the resin did not crystallize. Sufficient, the film stuck to the cast roll and could not be manufactured.

<Comparative example 3>
An attempt was made to produce a film in the same manner as in Example 1 except that the resin discharged from the T-die was brought into contact with a cast roll whose temperature was adjusted to 30 ° C. for 2.2 seconds, but the temperature of the cast roll was the crystal growth of the resin. The temperature was off, the crystallization of the resin due to contact with the cast roll was insufficient, and the film stuck to the cast roll, making it impossible to manufacture.

In Examples 1 to 5, it was possible to produce a resin film which was long and thin, wide, had high film thickness accuracy in the width direction, and had a good appearance, and the obtained film was subjected to thermoforming. The moldability at the time was good. However, in Example 5 in which the temperature of the cast roll was set to a relatively high temperature of 55 ° C., the film was partially stuck to the cast roll, and the cast roll peeling mark remained on the film.
In Comparative Example 1, the film was formed by sandwiching the film directly under the T-die with the cooling rolls facing each other and sandwiching the film from both sides, and the film was formed directly under the T-die with the crystallization not sufficiently progressing. Since both sides of the film were pressurized, the value of film thickness accuracy (± μm) × A was 9.1, and the film thickness accuracy was deteriorated as compared with Examples 1 to 5.
In Comparative Example 2, the contact time of the cast roll was set as short as 2.0 seconds, the crystallization of the resin was insufficient, the film was stuck to the cast roll, and the film could not be manufactured.
In Comparative Example 3, since the temperature of the cast roll is as low as 30 ° C. and deviates from the crystal growth temperature of the resin, the crystallization of the resin becomes insufficient, the film sticks to the cast roll, and the film can be manufactured. There wasn't.

11 T-die 12 Film-shaped molten resin 13 Cooling roll 14 Sanding roll

Claims (7)

Consists of poly (3-hydroxybutyrate) resin,
A resin film having a width of 500 mm or more, a length of 100 m or more, a film thickness of 20 to 500 μm, and a film thickness accuracy (± μm) × A in the width direction of 8 or less.
However, A is a numerical value calculated from the formula: (1+ (200-film thickness (μm)) × 0.002). The resin film according to claim 1, wherein the resin film is wound in a roll shape. The resin film according to claim 1 or 2, wherein the resin film has a total haze (%) / film thickness (μm) ratio of less than 0.3. The resin film according to any one of claims 1 to 3, wherein the poly (3-hydroxybutyrate) resin contains poly (3-hydroxybutyrate-co-3-hydroxyhexanoate). The method for producing a resin film according to any one of claims 1 to 4.
A step of melting the poly (3-hydroxybutyrate) resin in an extruder and continuously extruding a film-like molten resin from a T-die, and
The process includes a step of transporting the film-shaped molten resin while bringing one side of the film-shaped molten resin into contact with a cooling roll or an endless belt arranged under the T-die.
The set temperature of the cooling roll or the endless belt is 40 to 60 ° C.
A manufacturing method in which the contact time between the film-shaped molten resin and the cooling roll or endless belt is 2.2 seconds or longer. A molded product obtained by cutting out the resin film according to any one of claims 1 to 4 as necessary and subjecting it to thermoforming. The molded product according to claim 6, wherein at least a part thereof is provided with a three-dimensional shape.

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