JP6881151B2 - Deep-drawing film and deep-drawing packaging - Google Patents

Description

The present invention relates to a deep-drawing film and a deep-drawing package, and relates to a deep-drawing film and a deep-drawing package that can be suitably used for food packaging such as sliced ham and sliced bacon.

Conventionally, a multilayer film for deep-drawing packaging used for molding a deep-drawing package for packaging foods and the like has been proposed (see, for example, Patent Documents 1 to 6). In these multilayer films, a polyester resin layer, a gas barrier resin layer made of a nylon resin (Ny) or an ethylene-vinyl acetate copolymer saponified product (EVOH), and a polyolefin resin layer having a sealing property are laminated in this order. Has been done. In the films described in Patent Documents 1 to 4, the outer polyester resin layer is not an amorphous polyester resin layer obtained by copolymerization with cyclohexanedimethanol or a copolymerization with isophthalic acid, or a crystalline polyester. By using a polyethylene terephthalate resin layer solidified as a crystal, the waist, gloss and transparency required for the deeply squeezed package are imparted. Further, in the multilayer films described in Patent Documents 5 and 6, a multilayer film having a total film thickness of 300 μm or more and excellent impact resistance is realized.

Japanese Unexamined Patent Publication No. 7-096582 Japanese Unexamined Patent Publication No. 8-281892 Japanese Unexamined Patent Publication No. 2003-136648 Japanese Unexamined Patent Publication No. 2015-36196 Japanese Unexamined Patent Publication No. 10-100366 Japanese Unexamined Patent Publication No. 10-034852

In recent years, in the food industry, waste reduction and reduction of individual foods in consideration of environmental problems have been rapidly promoted with deepening consumer awareness. Even in deeply squeezed packaging for food packaging such as sliced ham and sliced bacon, it is required to reduce the weight by almost half of the thickness of the conventional packaging material, that is, to reduce the wall thickness while maintaining the quality of the packaging material. ing.

In the manufacturing process of a deep-drawing package for food packaging, a multilayer film of raw materials is supplied to a deep-drawing molding machine, and a bottom mold is formed into a desired shape and size with a molding die to form a plurality of deep-drawing portions on the multilayer film. Provide. Then, after filling each of the plurality of deeply drawn portions of the multilayer film with contents such as slice ham, a lid material film is supplied from the multilayer film filled with the contents, and the film is heat-sealed and vacuum-packed for cooling. Then, by cutting the film between the plurality of deep-drawn portions of the multilayer film, individual deep-drawn packages are manufactured. Then, in these deeply squeezed packages for food packaging, three to four individually manufactured deeply squeezed packages are shifted and laminated with a label tape in accordance with the reduction in the amount of food per individual package, and integrated. The so-called 3- to 4-series packs are manufactured.

In the manufacturing process of such a deep-drawn package, if the film for molding the deep-drawn package is thinned in accordance with the market demand, the strength and rigidity (waist) of the film are lowered, or the film is combined with the lid material. Curling may occur due to heat sealing. The decrease or deformation of the strength and rigidity of these individual packages not only reduces the commercial value of the deeply squeezed package including the contents including the appearance, but also molds and individually wraps the film in the manufacturing process of the deeply squeezed package. Workability such as aligned transportation of the body and orderly sticking of labels may be significantly deteriorated, and the production line may be stopped.

In response to such market demands, in the multilayer films of Patent Documents 1 to 3, the thickness of the multilayer film is set to 120 μm or more in order to give the film a waist, so that the thickness is insufficient when the film is thinned. As a result, the shape of the package may collapse. Further, in the multilayer film described in Patent Document 4, the film thickness is 60 μm to 75 μm, while the ratio of the thickness of the outer layer of the amorphous polyester resin layer to the film thickness is 15% or more and 25% or less. Therefore, the heat seal may cause curling.

Further, in the multilayer films described in Patent Documents 5 and 6, two types of polyester resin layers having a thickness of 200 μm to 500 μm are provided on the outer layer, and the thickness of the polyester resin layer is 8 with respect to the film thickness. By setting the ratio to 100 or more, the rigid property required for gas pack applications in which an inert gas is sealed and packaged together with the contents can be obtained. Therefore, it is difficult to form a film by simply thinning these multilayer films at the same ratio in terms of processing technology, and it is applied to market demands that require thinning, gas barrier properties, and pinhole resistance. It cannot be deployed.

Further, in these multilayer films, the amorphous polyester resin (hereinafter, also referred to as “PETG”) obtained by copolymerizing 1,4-cyclohexanedimethanol used for the outer layer does not have a melting point and has a glass transition temperature of 82 ° C. (hereinafter, also referred to as “PETG”). It has the property of softening when it exceeds Tg). Therefore, with the outer surface of the lid material in close contact with the hot plate, the seal box is raised from the bottom material side on which the multilayer film is molded, and the multilayer film is sandwiched between the rubber packing on the upper surface of the seal box and the hot plate. When heat sealing is performed at a temperature of 125 ° C. or higher, the PETG surface of the outer layer may adhere to the rubber packing of the seal box due to the sealing heat, and the glossiness of the PETG surface of the heat-sealed portion may deteriorate.

The present invention has been made in view of such circumstances, and has good rigidity and moldability, and even when the thickness is thinned, a deep-drawn package having excellent transparency and gloss can be obtained. It is an object of the present invention to provide a film for draw forming and a deep draw package.

As a result of diligent studies to solve the above problems, it was found that the above problems can be solved by a film for deep drawing forming having a predetermined heat resistance and a film thickness of a specific ratio, and the present invention has been completed. .. That is, the present invention is as follows.

The film for deep drawing according to the present invention has a first resin layer containing a heat-resistant polyester resin having a glass transition point (Tg) of 90 ° C. or higher as a main component, a second resin layer containing a polyethylene terephthalate resin, and a polyamide-based film. At least four layers of a third resin layer containing at least one resin as a main component selected from the group consisting of a resin and an ethylene-vinyl acetate copolymer saponified product and a fourth resin layer containing a polyolefin resin are these. The heat-resistant polyester-based resin, which is laminated in order, contains at least one type of diol component having a cyclic structure containing no double bond, and is a differential scanning calorimeter conforming to JIS-K7121. The amount of heat of crystal fusion ΔHm at the time of temperature rise measured under the condition of a temperature rise rate of 10 ° C./min is 20 J or less, the film thickness is 40 μm or more and 120 μm or less, and the thickness of the second resin layer with respect to the film thickness. The ratio is 30% or more and 75% or less.

In the film for deep drawing according to the present invention, the polyethylene terephthalate resin has a terephthalic acid content of 80 mol% or more in the polyvalent carboxylic acid component and a polyethylene glycol content in the polyhydric alcohol component. Is preferably 80 mol% or more.

In the deep drawing molding film according to the present invention, the third resin layer is a first layer containing a polyamide resin as a main component and a second layer containing an ethylene-vinyl acetate copolymer saponified resin as a main component. And are preferably included.

In the film for deep drawing molding according to the present invention, it is preferable that an adhesive resin layer containing a polyolefin-based adhesive resin is provided between the second resin layer and the third resin layer.

In the film for deep drawing molding according to the present invention, it is preferable that an adhesive resin layer containing a polyolefin-based adhesive resin is provided between the third resin layer and the fourth resin layer.

In the film for deep drawing molding according to the present invention, the fourth resin layer preferably has an easy peel strength of 0.8 N / 15 mm width or more and 4.0 N / 15 mm width or less.

The deep-drawing package according to the present invention is characterized by containing the above-mentioned deep-drawing film.

The deep-drawn package according to the present invention is preferably for food packaging.

According to the present invention, it is possible to realize a deep-drawing film and a deep-drawing package which have good rigidity and moldability and can obtain a deep-drawing package having excellent transparency and gloss even when thinned. it can.

FIG. 1 is a schematic cross-sectional view of a film for deep drawing according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view of a deep-drawn package according to an embodiment of the present invention.

Hereinafter, an embodiment of the present invention will be described in detail with reference to the accompanying drawings. The present invention is not limited to the following embodiments.

In the present embodiment, the "main component" means that the content of each component is preferably 50% by mass or more, more preferably 80, based on the entire resin component constituting each layer as a reference (100% by mass). It means that it contains mass% or more, more preferably 95% by mass or more, and particularly preferably 100% by mass.

(Film for deep drawing)
FIG. 1 is a schematic cross-sectional view of a film for deep drawing according to an embodiment of the present invention. As shown in FIG. 1, the deep draw forming film 1 has a heat-resistant resin layer (first resin layer) 11 containing a heat-resistant polyester resin having a glass transition point (Tg) of 90 ° C. or higher as a main component, and a heat-resistant resin layer. Provided on the polyethylene terephthalate resin layer (second resin layer) 12 mainly composed of the polyethylene terephthalate resin and the polyethylene terephthalate resin layer 12, the polyamide resin and the ethylene-vinyl acetate common weight are provided. A gas barrier resin layer (third resin layer) 13 containing at least one resin as a main component selected from the group consisting of coalesced saponified products, and a sealing resin layer provided on the gas barrier resin layer 13 and containing a polyolefin resin. (4th resin layer) 14 is provided. That is, the deep drawing film 1 is formed by laminating at least four layers of a heat-resistant resin layer 11, a polyethylene terephthalate resin layer 12, a gas barrier resin layer 13, and a sealing resin layer 14 in this order. An adhesive resin layer 15 is provided between the polyethylene terephthalate resin layer 12 and the gas barrier resin layer 13. An adhesive resin layer 16 is provided between the gas barrier resin layer 13 and the seal resin layer 14. The adhesive resin layers 15 and 16 do not necessarily have to be provided. Further, the gas barrier resin layer 13 may be composed of two or more layers. Similarly, the seal resin layer 14 may be composed of two or more layers.

The heat-resistant resin layer 11 has a crystal melting heat amount ΔHm at the time of temperature rise of 20 J or less, which is measured under the condition of a temperature rise rate of 10 ° C./min with a differential scanning calorimeter in accordance with JIS-K7121. Further, the heat-resistant resin layer 11 contains two or more kinds of diol components. The heat-resistant resin layer 11 has a cyclic structure in which at least one of the diol components does not contain a double bond.

The film 1 for deep drawing has a film thickness of 40 μm or more and 120 μm or less. When the film thickness of the deep drawing film 1 is 120 μm or less, the film formability is good, and when the film thickness is 40 μm or more, the rigidity and mechanical properties are good. The film thickness of the deep drawing film 1 is preferably 45 μm or more, more preferably 50 μm or more, further preferably 55 μm or more, further preferably 115 μm or less, and more preferably 110 μm or less from the viewpoint of further improving the above-mentioned effects. , 115 μm or less is more preferable.

Further, in the deep drawing forming film 1, the thickness ratio of the polyethylene terephthalate resin layer 12 to the film thickness is 30% or more and 75% or less. Since the thickness ratio of the polyethylene terephthalate resin layer 12 to the film thickness of the deep-drawing film 1 is 30% or more, good rigidity and curl resistance of the deep-drawing film 1 can be obtained. Further, in the deep drawing film 1, the thickness ratio of the polyethylene terephthalate resin layer 12 to the film thickness is 75% or less, so that the thickness of the gas barrier resin layer 13 and the seal resin layer 14 can be sufficiently secured. The gas barrier property and heat seal property are improved. Hereinafter, various components of the deep drawing film 1 will be described in detail.

(Heat-resistant resin layer 11 [first resin layer])
The heat-resistant resin layer 11 contains a heat-resistant polyester resin as a main component, and is provided as the outermost layer of the deep-draw molding film 1. The heat-resistant polyester-based resin is a polyester-based resin in which the heat of crystal melting ΔHm at the time of temperature rise is 20 J / g or less at a temperature rise rate of 10 ° C./min with a differential scanning calorimeter conforming to JIS-K7121. Contains two or more types of diol components. Further, the heat-resistant polyester resin has a cyclic structure in which at least one kind of diol component does not contain a double bond. As the cyclic structure, a cyclic structure having a 3-membered ring or more and a 10-membered ring or less is preferable, and a cyclic structure having a 4-membered ring or more and a 6-membered ring or less is more preferable. Further, as the cyclic structure, the cyclic structure may contain an oxygen atom derived from an ether bond.

The diol component having a cyclic structure in the heat-resistant polyester resin is preferably a bulky diol component. Examples of such a bulky diol component include spiroglycol, tetramethylcyclobutanediol (hereinafter, also referred to as “TMCD”), tricyclodecanedimethanol, isosorbide, and the like. One of these diol components may be used alone, or two or more thereof may be used in combination. Among these, as a bulky diol component, the glass transition temperature of the heat-resistant polyester resin becomes high, and it is possible to prevent the appearance from being deteriorated due to the adhesion of hot plate marks or whitening on the sealed portion at the time of heat sealing. At least one selected from the group consisting of spiroglycol, TMCD and isosorbide is preferred.

Examples of the diol component other than the bulky diol component in the heat-resistant polyester resin include diethylene glycol, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, and the like. 1,4-Butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, p- Examples thereof include xylenediol, bisphenol A, tetrabromobisphenol A and tetrabromobisphenol A-bis (2-hydroxyethyl ether). One of these diol components may be used alone, or two or more thereof may be used in combination. Among these, ethylene glycol is preferable as the diol component other than the bulky diol component from the viewpoint of being industrially inexpensive and easy to control the crystallinity and the glass transition temperature. Further, as the diol component other than the bulky diol component, the glass transition temperature of the heat-resistant polyester resin is not increased, but from the viewpoint of improving the impact resistance and transparency of the heat-resistant polyester resin, 1,4- Cyclohexanedimethanol is preferred.

The content of the bulky diol component in the heat-resistant polyester resin is preferably 20 mol% or more, more preferably 30 mol% or more, based on the total diol component contained in the heat-resistant polyester resin. It is more preferably 40 mol% or more. The upper limit of the content ratio of the bulky diol component is not particularly limited, but is preferably 70 mol% or less. If the content of the bulky diol component in the heat-resistant polyester resin is 20 mol% or more, the glass transition temperature of the heat-resistant polyester resin is raised to deteriorate the appearance due to adhesion of hot plate marks or whitening during heat sealing. Can be prevented. Further, if the content of the bulky diol component in the heat-resistant polyester resin is 70 mol% or less, there is no possibility that problems such as impaired fluidity at the time of melting will occur.

Examples of the dicarboxylic acid component used in the heat-resistant polyester resin include terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stillbenzdicarboxylic acid, and 4,4. -Biphenyldicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracendicarboxylic acid, 4,4-diphenyletherdicarboxylic acid, 4,4-di Aromatic dicarboxylic acids such as phenoxyetanedicarboxylic acid, 5-Nasulfoisophthalic acid and ethylene-bis-p-benzoic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid and 1, Examples thereof include aliphatic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid. One of these dicarboxylic acid components may be used alone, or two or more thereof may be used in combination. Among these, terephthalic acid and isophthalic acid are preferable as the dicarboxylic acid component from the viewpoint of being industrially inexpensive and the synthesized heat-resistant polyester resin being chemically stable.

The ultimate viscosity (IV) of the heat-resistant polyester resin is not particularly limited. The ultimate viscosity (IV) of the heat-resistant polyester resin is preferably 0.4 dl / g or more and 1.0 dl / g or less, and more preferably 0.5 dl / g or more and 0.9 or less. When the ultimate viscosity (IV) is 0.4 dl / g or more and 1.0 dl / g or less, both the mechanical strength of the film and the fluidity at the time of melting can be compatible.

The glass transition temperature of the heat-resistant polyester resin is measured by a differential scanning calorimeter according to JIS-K7121. The glass transition temperature of the heat-resistant polyester resin is 90 ° C. or higher, preferably 95 ° C. or higher, and more preferably 100 ° C. or higher. The upper limit of the glass transition temperature is not particularly limited, but is preferably 130 ° C. or lower. If the glass transition temperature of the heat-resistant polyester resin is 90 ° C. or higher, there is no risk of deterioration of the appearance due to adhesion of hot plate marks or whitening on the sealed portion during heat sealing. The glass transition temperature of the heat-resistant polyester resin can be appropriately adjusted to a preferable range by adjusting the copolymerization component.

The heat-resistant polyester resin is a differential scanning calorimeter conforming to JIS-K7121, and the amount of heat of crystal melting ΔHm at the time of temperature rise at a temperature rise rate of 10 ° C./min is 20 J / g or less, preferably 15 J / g or less. 10 J / g or less is more preferable, and 5 J / g or less is further preferable. When the heat of fusion for crystallization of the heat-resistant polyester resin ΔHm is 20 J / g or less, the transparency does not decrease or the moldability does not deteriorate due to crystallization. The heat-resistant polyester resin has no limitation on the lower limit of the amount of heat of crystal fusion ΔHm, and is, for example, 0 J / g or more.

As the heat-resistant polyester resin, various commercially available raw materials can be preferably used. Examples of the heat-resistant polyester resin include a trade name: "ALTESTER" (manufactured by Mitsubishi Gas Chemical Co., Ltd., a spiroglycol copolymerized polyester resin) and a trade name: "TRITAN" (manufactured by EASTMAN Chemical Co., Ltd., a TMCD copolymerized polyester resin). And so on.

The thickness of the heat-resistant resin layer 11 is not particularly limited. The thickness of the heat-resistant resin layer 11 is preferably 1 μm or more, more preferably 3 μm or more, further preferably 5 μm or more, still more preferably 20 μm or less, still more preferably 15 μm or less, still more preferably 10 μm or less. If the thickness of the heat-resistant resin layer 11 is 1 μm or more, whitening during heat sealing can be prevented and a good appearance can be obtained. Further, if the thickness of the heat-resistant resin layer 11 is 20 μm or less, another layer such as a polyethylene terephthalate resin can be further arranged, and good curl resistance and barrier property can be imparted.

Further, from the viewpoint of heat resistance, rigidity and moldability, the heat-resistant resin layer 11 preferably has a thickness ratio of 1% or more, preferably 1.5% or more, to the film thickness of the deep drawing molding film 1. It is more preferably 2% or more, more preferably 10% or less, preferably 8% or less, still more preferably 6% or less.

Further, from the viewpoint of heat resistance, rigidity and moldability, the heat-resistant resin layer 11 preferably has a thickness ratio of 1% or more, preferably 2% or more, with respect to the thickness of the polyethylene terephthalate resin layer 12. More preferably, it is 3% or more, further preferably 15% or less, preferably 13% or less, and further preferably 11% or less.

(Polyethylene terephthalate resin (PET resin) layer 12 [second resin layer])
The film 1 for deep drawing is laminated with a polyethylene terephthalate resin layer 12 adjacent to the inside of the heat-resistant resin layer 11 which is the outermost layer. The polyethylene terephthalate resin layer 12 is made of a polyethylene terephthalate resin. Sometimes it is solidified in an amorphous state to form a layer. By laminating the polyethylene terephthalate resin layer 12 adjacent to the inside of the heat-resistant resin layer 11, it is possible to impart rigidity, strength, moldability and gloss to the deep-draw molding film 1.

The polyethylene terephthalate resin contained in the polyethylene terephthalate resin layer 12 is obtained by polymerizing a polyvalent carboxylic acid component and a polyhydric alcohol component, which are monomer components.

As the polyvalent carboxylic acid component, for example, terephthalic acid, aromatic dicarboxylic acid, aliphatic dicarboxylic acid, alicyclic dicarboxylic acid and the like constituting an ethylene terephthalate unit are used. One type of polyvalent carboxylic acid component may be used alone, or two or more types may be used in combination.

Examples of the aromatic dicarboxylic acid include benzenedicarboxylic acids such as isophthalic acid, orthophthalic acid and 5-tert-butylisophthalic acid, naphthalenedicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, 4,4'-dicarboxydiphenyl and Dicarboxybiphenyls such as 2,2,6,6-tetramethylbiphenyl-4,4'-dicarboxylic acid, 1,1,3-trimethyl-3-phenylinden-4,5-dicarboxylic acid and its substitutes; Examples thereof include 1,2-diphenoxyetane-4,4'-dicarboxylic acid and its substitutes.

Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebatic acid, pimeric acid, suberic acid, undecanoic acid, dodecandicarboxylic acid, brush phosphate, tetradecanediocarboxylic acid, Examples thereof include tapsinic acid, nonadecandicarboxylic acid and docosandicarboxylic acid.

Examples of the alicyclic dicarboxylic acid include 1,4-dicarboxycyclohexane and 1,3-dicarboxycyclohexane.

As the polyhydric alcohol component, ethylene glycol, an aliphatic diol, an alicyclic diol, an aromatic diol and the like constituting a polyethylene terephthalate unit can be used. One of these polyhydric alcohol components may be used alone, or two or more thereof may be used in combination.

As the aliphatic diol, diethylene glycol, propylene glycol, butanediol, 1,6-hexanediol, 1,10-decanediol, neopentyl glycol, 2-methyl-2-ethyl-1,3-propanediol 2-diethyl- Examples thereof include 1,3-propanediol, 2-ethyl-2-n-butyl-1,3-propanediol, 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol.

Examples of the aromatic diol include ethylene oxide adducts of bisphenol compounds such as 2,2-bis (4'-β-hydroxyethoxydiphenyl) propane and bis (4'-β-hydroxyethoxyphenyl) sulfone, and xylylene glycol. Can be mentioned.

Further, as the above-mentioned polyvalent carboxylic acid component and polyhydric alcohol component, one or more kinds of polyvalent carboxylic acid components and one or more kinds of polyhydric alcohol components can be appropriately combined and used. The type and content of the combination of these monomer components can be appropriately determined based on the desired film characteristics and economic efficiency of the deep drawing film 1.

As the polyethylene terephthalate resin, the content of terephthalic acid in the polyvalent carboxylic acid component is preferably 80 mol% or more, and preferably 83 mol% or more. Further, as the polyethylene terephthalate resin, the content of polyethylene glycol in the polyhydric alcohol component is preferably 80 mol% or more, and more preferably 83 mol% or more. The polyethylene terephthalate resin contains 80 mol% or more of terephthalic acid in the polyvalent carboxylic acid component and 80 mol% or more of polyethylene glycol in the polyhydric alcohol component, thereby forming a film for deep drawing. The rigidity of 1 becomes larger, and the effect of suppressing curl of the film at the time of heat sealing becomes larger. Further, as the polyethylene terephthalate resin, the content of terephthalic acid in the polyvalent carboxylic acid component is preferably 95 mol% or less, preferably 90 mol% or less, from the viewpoint of economy. As the polyethylene terephthalate resin, the content of polyethylene glycol in the polyhydric alcohol component is preferably 95 mol% or less, and preferably 90 mol% or less, from the viewpoint of economy.

Further, as the polyethylene terephthalate resin, one kind of polyethylene terephthalate resin may be used alone, or two or more kinds of polyethylene terephthalate resins may be used in combination.

Further, as the polyethylene terephthalate resin, from the viewpoint of economy, homopolyethylene terephthalate composed of terephthalic acid and ethylene glycol, a polyvalent carboxylic acid component other than terephthalic acid and ethylene glycol, and a polyhydric alcohol component are each 5 mol% or less. Copolymerized polyethylene terephthalate-based copolymerized polyester resin and the like are preferable.

As for the thickness of the polyethylene terephthalate resin layer 12, the thickness ratio of the entire film 1 for deep drawing molding to the film thickness is 30% or more, preferably 35% or more, more preferably 40% or more, and 75%. % Or less, preferably 70% or less, and more preferably 65% or less. As for the thickness of the polyethylene terephthalate resin layer 12, if the thickness ratio to the film thickness of the entire deep draw forming film 1 is 30% or more, the good rigidity and curl resistance of the deep draw forming film 1 are obtained. When it is 75% or less, the thickness of the gas barrier resin layer 13 and the seal resin layer 14 can be sufficiently secured, and the gas barrier property and the heat seal property are improved.

The thickness of the polyethylene terephthalate resin layer 12 is preferably 15 μm or more, more preferably 17.5 μm or more, further preferably 20 μm or more, still more preferably 70 μm or less, still more preferably 60 μm or less, from the viewpoint of rigidity and moldability. 55 μm or less is more preferable.

(Gas barrier resin layer 13 [third resin layer])
The gas barrier resin layer 13 imparts oxygen gas barrier properties to the deep drawing forming film 1. By providing the gas barrier resin layer 13, the deep-draw molding film 1 can prevent oxygen from permeating the contents of the deep-draw package into food and the like, and prevent the food and the like from spoiling.

The gas barrier resin layer 13 is made of at least one resin selected from the group consisting of a polyamide resin (hereinafter, also referred to as “PA”) and an ethylene-vinyl acetate copolymer saponified product (hereinafter, also referred to as “EVOH”). It is contained as a main component. The gas barrier resin layer 13 may be, for example, a gas barrier resin layer 13 containing PA as a main component, a gas barrier resin layer 13 containing EVOH as a main component, and a mixed resin of PA and EVOH as a main component. The gas barrier resin layer 13 may be used. Further, the gas barrier resin layer 13 may be a single layer or may be a multilayer in which a plurality of gas barrier resin layers 13 are laminated. Examples of the multilayer gas barrier resin layer 13 include a laminate of a first gas barrier resin layer 13 containing PA as a main component and a second gas barrier resin layer 13 containing EVOH as a main component.

The polyamide-based resin is not particularly limited, but a nylon-based resin (hereinafter, also referred to as “Ny”) is preferable from the viewpoint of gas barrier property and pinhole resistance. Examples of nylon-based resins include polymers of condensation units such as 6 nylon, 66 nylon, 69 nylon, 6-66 nylon, 12 nylon, 11 nylon, 610 nylon, 612 nylon, 6I-6T nylon and MXD6 nylon, and , Two or more kinds of these copolymers and a mixture thereof and the like can be mentioned. Further, these nylon-based resins may be used alone or in combination of two or more. Among these, as the nylon-based resin, MXD6 nylon is preferable from the viewpoint of gas barrier property, and 6 nylon and 6-66 nylon are preferable from the viewpoint of pinhole resistance.

The EVOH preferably has an ethylene content of 30 mol% or more and 60 mol% or less from the viewpoint of moldability and gas barrier properties. Further, the EVOH preferably has a saponification degree of 95% or more from the viewpoint of moldability and gas barrier property.

When the gas barrier resin layer 13 containing PA as a main component is provided, the thickness of the gas barrier resin layer 13 is preferably 2 μm or more, more preferably 3 μm or more, and further preferably 5 μm or more. Further, it is preferably 25 μm or less, more preferably 20 μm or less, and further preferably 15 μm or less. If the thickness of the gas barrier resin layer 13 is 2 μm or more, good gas barrier properties and pinhole resistance can be obtained, and if it is 25 μm or less, good cutability in a deep drawing packaging machine can be obtained.

When the gas barrier resin layer 13 containing EVOH as a main component is provided, the thickness of the gas barrier resin layer 13 is preferably 1 μm or more, more preferably 2 μm or more, and preferably 20 μm or less. It is more preferably 10 μm or less. If the thickness of the gas barrier resin layer 13 is 1 μm or more, good oxygen gas barrier properties can be obtained, and if it is 20 μm or less, good pinhole properties can be obtained.

From the viewpoint of oxygen permeability, rigidity and moldability, the gas barrier resin layer 13 preferably has a thickness ratio of 10% or more, more preferably 12% or more, based on the thickness of the polyethylene terephthalate resin layer 12. It is preferably 14% or more, more preferably 40% or less, preferably 37.5% or less, and even more preferably 35% or less.

(Seal resin layer 14 [fourth resin layer])
The seal resin layer 14 imparts flexibility and sealability to the deep drawing forming film 1. The seal resin layer 14 contains an olefin resin. Examples of the olefin resin include ethylene-vinyl acetate copolymer (hereinafter, also referred to as “EVA”) and polyethylene (hereinafter, also referred to as “PE”). As the seal resin layer 14, the seal resin layer 14 containing EVA as a main component may be used, or the seal resin layer 14 containing PE as a main component may be used.

The ethylene content of EVA is not particularly limited. The ethylene content of EVA is preferably 1.5 mol% or more and 20 mol% or less, and 3 mol% or more and 15 mol% or less, from the viewpoint of film forming stability of the deep drawing film 1. Is more preferable.

The PE is not particularly limited. Examples of PE include low-density polyethylene (hereinafter, also referred to as “LDPE”), linear low-density polyethylene (hereinafter, also referred to as “LLDPE”), high-density polyethylene (hereinafter, also referred to as “HDPE”), and A mixture of these is used.

The thickness of the seal resin layer 14 is preferably 0.5 μm or more, more preferably 1 μm or more, still more preferably 1.5 μm or more, from the viewpoint of heat sealability, rigidity and moldability. Further, it is preferably 30 μm or less, more preferably 27.5 μm or less, and further preferably 25 μm or less.

From the viewpoint of heat sealability, rigidity and moldability, the thickness ratio of the polyethylene terephthalate resin layer 12 to the thickness of the seal resin layer 14 is preferably 5% or more, preferably 6% or more. More preferably, it is more preferably 7% or more, further preferably 50% or less, preferably 47.5% or less, and further preferably 45% or less.

Further, the seal resin layer 14 may be a single layer or a laminated layer. The multilayer sealing resin layer 14 includes, for example, a polyolefin-based resin layer containing a polyolefin-based resin as a main component and a polyolefin-based resin layer having an easy peel (hereinafter, also referred to as “EP”) function (hereinafter, “EP layer”). ”).

The resin having an easy peel function is not particularly limited, and examples thereof include a mixed resin of two incompatible polyolefin resins. Examples of the mixed resin include a mixed resin of LLDPE and polybutene (hereinafter, also referred to as “PB”), a mixed resin of EVA and polypropylene (hereinafter, also referred to as “PP”), a mixed resin of PP and LDPE, and PP. A mixed resin of and ionomer (hereinafter, also referred to as "IO"), a mixed resin of PP and an ethylene-acrylic acid copolymer (hereinafter, also referred to as "EAA"), and a PP and an ethylene-methyl methacrylate copolymer. Examples thereof include a mixed resin with (hereinafter, also referred to as “EMMA”). Among these, as the mixed resin, a mixed resin of LLDPE and PB and a mixed resin of PP and LDPE are preferable from the viewpoint of the easy peel function.

The mixed resin preferably contains 35% by mass or more of both of the two incompatible polyolefin resins from the viewpoint of obtaining good opening properties of the deeply drawn package by the easy peel function.

The thickness of the EP layer is preferably 2 μm or more, more preferably 3 μm or more, further preferably 4 μm or more, preferably 15 μm or less, and more preferably 12 μm or less. It is more preferably 10 μm or less. If the thickness of the EP layer is 2 μm or more, the stable film-forming property of the deep drawing film 1 can be obtained. Further, when the thickness is 15 μm or less, fluffing and film residue can be less likely to occur at the time of peeling, and a good peeled appearance can be obtained.

The easy peel strength (peeling strength) of the seal resin layer 14 may be such that cohesive failure occurs when the deeply drawn package is peeled off and the peeled surface does not fluff. The easy peel strength of the seal resin layer 14 is, for example, preferably 0.8 N / 15 mm width or more, more preferably 1.0 N / 15 mm width or more, and 1.2 N / 15 mm width at 25 ° C. It is more preferably 4.0 N / 15 mm width or less, more preferably 3.5 N / 15 mm width or less, and further preferably 3.0 N / 15 mm width or less. If the easy peel strength is 0.8 N / 15 mm width or more, it is possible to prevent abnormalities such as the seal coming off during transportation of the deep drawn package, and if it is 4.0 N / 15 mm width or less, the deep drawn package is deep drawn. Good openability of the package can be obtained.

(Adhesive resin layers 15, 16)
The deep drawing forming film 1 may be provided with an adhesive resin layer containing an adhesive resin between each layer. For example, the film 1 for deep drawing may be provided with at least one adhesive resin layer 15 between the polyethylene terephthalate resin layer 12 and the gas barrier resin layer 13, and the seal resin layer 14 and the gas barrier resin layer 13 may be provided. At least one adhesive resin layer 16 may be provided between them. Further, from the viewpoint of further enhancing the interlayer adhesion strength, the film 1 for deep drawing is, for example, between the EVOH layer and the PE layer, between the PA layer and the PE layer, and between the polyethylene terephthalate resin layer and the EVOH layer. , An adhesive resin layer may be provided between the polyethylene terephthalate resin layer and the PA layer.

The adhesive resin is not particularly limited as long as the various resin layers constituting each layer can be adhered with a required strength. As the adhesive resin, a polyolefin-based resin modified with an unsaturated carboxylic acid or a derivative thereof is preferable. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and citraconic acid.

Further, as the adhesive resin, an ester of unsaturated carboxylic acid and an anhydride may also be used. The adhesive resin includes methyl acrylate, methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, butyl methacrylate, vinyl acetate, glycidyl acrylate, glycidyl methacrylate, acrylamide, methacrylamide and sodium acrylate as derivatives. Etc. may be used.

As the adhesive resin, for example, a commercially available product such as a trade name: Admer (manufactured by Mitsui Chemicals, Inc.) can be preferably used. Among these, as the adhesive resin, a special polyolefin-based adhesive resin and a polyethylene elastomer-based adhesive resin are useful when the PP layer, PE layer, EVOH layer and polyethylene terephthalate resin layer 12 are adhered to each other. Further, as the adhesive resin, when the EVOH layer, the PP layer and the PE layer are bonded, an LLDPE type or a PP type can be preferably used.

In the film 1 for deep drawing, for example, each layer is made of a heat-resistant polyester resin (A), a polyethylene terephthalate resin layer (B), a PA layer (C), an EVOH layer (D), an EVA layer or a PE layer by using abbreviations. When represented by (E), the easy peel layer (F), and the adhesive resin layer (G), the following layer structure can be formed.
(1) A / B / G / C / D / G / E
(2) A / B / G / D / C / G / E
(3) A / B / G / C / D / C / G / E
(4) A / B / G / C / G / D / G / E
(5) A / B / G / C / D / G / F
(6) A / B / G / C / D / G / E / F
(7) A / B / G / D / C / G / E / F
(8) A / B / G / D / C / G / F
(9) A / B / G / C / D / C / G / E / F
(10) A / B / G / C / G / D / G / E / F

Among the above layer structures, the deep drawing film 1 preferably has the layer structures (1), (2), (3), (5), (6), (7) and (9), and (6). , (7) and (9) are preferable.

The film 1 for deep drawing can be produced by using a conventionally known method. The deep drawing film 1 can be produced by, for example, an extrusion lamination method, a coextrusion inflation method, a coextrusion T-die method, or the like. Among these, it is preferable to use the coextrusion T-die method as a method for producing the film 1 for deep drawing.

As described above, according to the film 1 for deep drawing according to the above embodiment, the heat of fusion of crystallization of the heat-resistant polyester resin ΔHm is 20 J / g or less, so that the transparency is increased by crystallization during heat sealing. It does not deteriorate or the moldability does not deteriorate. Further, since the film 1 for deep drawing molding has a film thickness of 40 μm or more and 120 μm or less, the formability of the film is improved, and the rigidity and mechanical properties are also improved. Further, in the film 1 for deep drawing, the thickness ratio of the polyethylene terephthalate resin layer 12 to the film thickness is 30% or more and 75% or less, so that rigidity and curl resistance can be obtained, and the gas barrier resin layer 13 and the seal can be obtained. A sufficient thickness of the resin layer 14 can be secured, and the gas barrier property and the heat seal property are improved. Therefore, it is possible to realize a deep-draw molding film 1 which has good rigidity and moldability and can obtain a deep-draw package having excellent transparency and gloss even when the wall thickness is thinned.

(Deep drawing package)
The film 1 for deep drawing molding according to the above embodiment can be used for a deep drawing package by molding. FIG. 2 is a schematic cross-sectional view of the deep-drawn package 2 according to the embodiment of the present invention. As shown in FIG. 2, the deep-drawing package 2 includes a bottom material 21 obtained by deep-drawing the film 1 for deep-drawing according to the above embodiment, and a lid material 22 provided so as to cover the bottom material 21. To be equipped. The bottom material 21 is provided with a bottom portion 21A having a predetermined depth in the central portion by deep drawing. Contents such as food are housed in the bottom 21A. Further, in the bottom material 21, the deep drawing forming film 1 is arranged so that the outer side of the bottom portion 21A is the heat-resistant resin layer 11 and the inner side is the sealing resin layer 14. In the bottom material 21, the sealing resin layer 14 of the outer edge portion (sealing portion) 21B is adhered to the lid material 22 by heat sealing. As described above, by using the deep-drawing film 1 as the bottom material 21 of the deep-drawing package 2, the rigidity and moldability are good, and even when the thickness is thinned, the transparency and glossiness are excellent. A deep-drawn package 2 can be obtained.

The lid material 22 is not particularly limited as long as it has an easy peeling property. As the lid material 22, for example, a stretched polypropylene resin film (hereinafter, also referred to as “OPP”), a transparent vapor-deposited polyethylene terephthalate film, and an LLDPE film are dry-laminated, and a stretched polyethylene terephthalate (hereinafter, also referred to as “OPET”). A laminate obtained by dry-laminating a film and a coextruded film containing EVOH or Ny and having LLDPE as a sealing layer can be used.

Hereinafter, the present invention will be described in more detail based on examples carried out to clarify the effects of the present invention. The present invention is not limited to the following examples and comparative examples.

(Example 1)
The following layer structure (first resin layer / second resin layer / adhesive resin layer / third resin layer A / third resin layer B / adhesive resin layer / fourth resin layer A / fourth resin) by the coextrusion T-die method A film for deep drawing having layer B) was produced. The film thickness was 60 μm.
Heat resistant polyester 1 (3 μm) / PET (30 μm) / adhesive resin (4 μm) / Ny (5 μm) / EVOH1 (5 μm) / adhesive resin (4 μm) / LLDPE (5 μm) / EP1 (4 μm)
Heat-resistant polyester 1: TMCD copolymerized polyester resin, trade name: "TRITAN" (Tg: 116 ° C, ΔHm: 0J / g)
PET: Polyethylene terephthalate resin, polyethylene terephthalate homopolymer (Tg: 72 ° C, ΔHm: 30J / g)
Adhesive resin: Unsaturated carboxylic acid-modified polyolefin resin Ny: 6-66 Copolymerized nylon Nylon 66 Ratio 15%
EVOH1: Ethylene-vinyl acetate copolymer saponified product Ethylene 38 mol%
LLDPE: Linear low density polyethylene EP1: Mixing of linear low density polyethylene (50%) and polybutene (50%)

Using a deep drawing packaging machine (model number "FV6300", manufactured by Omori Machinery Co., Ltd.), the obtained film for deep drawing molding has a diameter of 98 mm and a drawing depth under the conditions of a molding heating temperature of 90 ° C. and a molding time of 1.5 seconds. A 5 mm, columnar bottom was provided to form a bottom material film. Next, a sliced ham having a diameter of 95 mm and a diameter of 35 g is filled in the bottom, the following lid material is covered with a film for the bottom material, heat-sealed at 140 ° C. × 2.0 seconds, and then vacuum-packed to a length of 100 mm and a width of 100 mm. An 80 mm deeply drawn package was prepared.
As the lid material, the following laminated body produced by the dry laminating method was used. In the following, "//" represents adhesion by the dry laminating method.
OPP (30 μm) // Transparent vapor deposition PET (12 μm) // LLDPE (40 μm)
OPP: Biaxially stretched polypropylene film Transparent vapor deposition PET: VM-PET manufactured by Toyo Melalizing
LLDPE: Linear low density polyethylene film

(Example 2)
The film for deep drawing has the following layer structure (first resin layer / second resin layer / adhesive resin layer / third resin layer / adhesive resin layer / fourth resin layer A / fourth resin layer B), and the film thickness. A deeply squeezed package was produced in the same manner as in Example 1 except that the thickness was set to 100 μm.
Heat-resistant polyester 2 (5 μm) / PET (50 μm) / adhesive resin (10 μm) / EVOH2 (10 μm) / adhesive resin (10 μm) / EVA (21 μm) / EP2 (4 μm)
Heat-resistant polyester 2: Spiroglycol copolymerized polyester resin, trade name: "ALTESTER" (Tg: 101 ° C, ΔHm: 0J / g)
EVOH2: Ethylene-vinyl acetate copolymer saponified ethylene 32 mol
EVA: Ethylene-vinyl acetate copolymer EP2: Mixing of linear low density polyethylene (60%) and polybutene (40%)

(Example 3)
The film for deep drawing is formed into the following layer structure (first resin layer / second resin layer / adhesive resin layer / third resin layer A / third resin layer B / adhesive resin layer / fourth resin layer A / fourth resin). A deeply squeezed package was produced in the same manner as in Example 1 except that the layer was B) and the film thickness was 40 μm.
Heat resistant polyester 1 (1 μm) / PET (24 μm) / adhesive resin (3 μm) / Ny (2 μm) / EVOH1 (3 μm) / adhesive resin (3 μm) / LLDPE (2 μm) / EP1 (2 μm)

(Example 4)
The film for deep drawing is formed into the following layer structure (first resin layer / second resin layer / adhesive resin layer / third resin layer A / fourth resin layer B / adhesive resin layer / fourth resin layer A / fourth resin). A deeply squeezed package was produced in the same manner as in Example 1 except that the layer B) was used and the film thickness was 60 μm.
Heat resistant polyester 3 (3 μm) / PET (40 μm) / adhesive resin (3 μm) / Ny (3 μm) / EVOH1 (3 μm) / adhesive resin (3 μm) / LLDPE (3 μm) / EP1 (2 μm)
Heat-resistant polyester 3: Spiroglycol copolymerized polyester resin, trade name: "ALTESTER" (Tg: 116 ° C, ΔHm: 0J / g)

(Comparative Example 1)
The film for deep drawing is formed into the following layer structure (PETG layer (second resin layer) / adhesive resin layer / third resin layer A / third resin layer B / adhesive resin layer / fourth resin layer A / fourth resin layer. B), a deeply drawn package was produced in the same manner as in Example 1 except that the film thickness was 60 μm.
PETG (33 μm) / Adhesive resin (4 μm) / Ny (5 μm) / EVOH1 (5 μm) / Adhesive resin (4 μm) / LLDPE (5 μm) / EP1 (4 μm)
PETG: 1,4-Cyclohexanedimethanol copolymerized polyester resin (Tg: 82 ° C., ΔHm: 0J / g)

(Comparative Example 2)
The film for deep drawing is formed into the following layer structure (first resin layer / second resin layer / adhesive resin layer / third resin layer A / third resin layer B / adhesive resin layer / fourth resin layer A / fourth resin). A deeply squeezed package was produced in the same manner as in Example 1 except that the layer B) was used and the film thickness was 60 μm.
Heat resistant polyester 1 (3 μm) / PET (10 μm) / adhesive resin (5 μm) / Ny (6 μm) / EVOH1 (8 μm) / adhesive resin (5 μm) / LLDPE (18 μm) / EP3 (5 μm)
EP3: Mixing of linear low density polyethylene (70%) and polybutene (30%)

(Comparative Example 3)
The film for deep drawing is formed into the following layer structure (first resin layer / second resin layer / adhesive resin layer / third resin layer A / third resin layer B / adhesive resin layer / fourth resin layer A / fourth resin). A deeply squeezed package was produced in the same manner as in Example 1 except that the layer B) was used and the film thickness was 60 μm.
Heat resistant polyester 2 (20 μm) / PET (17 μm) / adhesive resin (4 μm) / Ny (3 μm) / EVOH1 (4 μm) / adhesive resin (4 μm) / LLDPE (3 μm) / EP1 (5 μm)

(Comparative Example 4)
The film for deep drawing is formed into the following layer structure (PETG layer (fourth resin layer) / second resin layer / adhesive resin layer / third resin layer A / third resin layer B / adhesive resin layer / fourth resin layer A. / A deeply drawn package was produced in the same manner as in Example 1 except that the fourth resin layer B) was used and the film thickness was 60 μm.
PETG (3 μm) / PET (30 μm) / Adhesive resin (4 μm) / Ny (5 μm) /
EVOH1 (5 μm) / Adhesive resin (4 μm) / LLDPE (5 μm) / EP1 (4 μm)

(Comparative Example 5)
The film for deep drawing has the following layer structure (first resin layer / second resin layer / adhesive resin layer / third resin layer A / third resin layer B / adhesive resin layer / fourth resin layer), and the film thickness. A deeply drawn package was produced in the same manner as in Example 1 except that the thickness was set to 200 μm.
Heat-resistant polyester 3 (5 μm) / PET (140 μm) / adhesive resin (10 μm) / Ny (15 μm) / EVOH1 (10 μm) / adhesive resin (10 μm) / LLDPE (10 μm)

Next, the deep-drawn packages obtained in Examples 1 to 4 and Comparative Examples 1 to 5 were evaluated under the following conditions. The results are shown in Table 1 below.

(Evaluation of moldability)
The moldability of the deep-drawn package when molded into a cylindrical shape with a diameter of 98 mm and a drawing depth of 5 mm was evaluated under the conditions of a molding heating temperature of 90 ° C. and a molding time of 1.5 seconds. The evaluation criteria are shown below.
◯: Molded according to the mold ×: Could not be molded according to the mold

(Heat seal evaluation)
After the packaging was prepared, it was observed within 5 minutes, and the average value of the lifted heights of the curls at the four corners of the heat-sealed portion was measured and evaluated. The evaluation criteria are shown below.
◯: The lift height of the curl is less than 5 mm ×: The average lift height of the curl is 5 mm or more

<Appearance evaluation>
The appearance of the deep-drawn package was visually observed and evaluated. The evaluation criteria are shown below.
◯: The heat seal part was whitened and no trace of the seal hot plate was confirmed. ×: The heat seal part was whitened and the trace of the seal hot plate was confirmed.

<Easy peel strength (EP strength)>
A strip of 15 mm width was cut from four points on the top, bottom, left, and right of the deep-drawn package to prepare a test piece. The maximum load when the lid material and the bottom material were peeled off from the test piece with a tensile tester (manufactured by Intesco) at a peeling angle of 180 degrees and a speed of 200 mm / min was taken as the easy peel strength, and the average value of four points was calculated.

As can be seen from Table 1, according to Examples 1 to 4 according to the above-described embodiment, the curl of the heat-sealed portion of the deep-drawn package was less than 5 mm, and the deep-drawn package was easy to align. In addition, the appearance was good without whitening of the heat-sealed portion and no trace of the heat-sealed plate. Good easy peeling property (easy opening property) was also obtained.

On the other hand, in Comparative Examples 1 to 3, it was found that the curl of the heat-sealed portion of the package was 5 mm or more, and the deep-drawn package was not satisfactorily aligned and conveyed. This result is considered to be because the thickness of the polyethylene terephthalate resin layer 12 was too thin with respect to the film layer thickness. Further, in Comparative Example 1 and Comparative Example 4, the appearance of the package was deteriorated. It is probable that this result is because PETG is used for the outermost layer, so that the outermost layer is whitened at the time of heat sealing, and traces of the sealing hot plate are confirmed. Further, in Comparative Example 5, the moldability was deteriorated. This result is considered to be because the film thickness is 200 μm and the total film thickness is thick.

The present invention has the effect of realizing a film for deep drawing molding having good rigidity, curl resistance, moldability, etc. without impairing transparency and gloss, and for example, a deep drawing package for food packaging and the like. It can be suitably used in the above, and the volume of waste can be reduced to the extent that the current product is halved.

1 Deep-drawing film 2 Deep-drawing packaging 11 Heat-resistant resin layer (first resin layer)
12 Polyethylene terephthalate resin layer (second resin layer)
13 Gas barrier resin layer (third resin layer)
14 Seal resin layer (4th resin layer)
15, 16 Adhesive resin layer
21 Bottom material 21A Bottom 21B Outer edge (seal part)
22 Lid material

Claims (10)

A first resin layer containing a heat-resistant polyester resin having a glass transition point (Tg) of 90 ° C. or higher as a main component.
Second resin layer containing polyethylene terephthalate resin,
A third resin layer containing at least one resin as a main component selected from the group consisting of a polyamide resin and an ethylene-vinyl acetate copolymer saponified product, and at least four layers of a fourth resin layer containing a polyolefin resin. Are stacked in this order,
The heat-resistant polyester resin contains at least one type of diol component having a cyclic structure containing no double bond, and has a temperature rise rate of 10 ° C./10 ° C. in a differential scanning calorimeter conforming to JIS-K7121. The amount of heat of crystal fusion ΔHm at the time of temperature rise measured under the condition of minutes is 20 J / g or less.
A film for deep drawing molding, wherein the film thickness is 40 μm or more and 120 μm or less, and the thickness ratio of the second resin layer to the film thickness is 30% or more and 75% or less. The polyethylene terephthalate resin has a terephthalic acid content of 80 mol% or more in the polyvalent carboxylic acid component and a polyethylene glycol content of 80 mol% or more in the polyhydric alcohol component, according to claim 1. The film for deep drawing molding described. According to claim 1 or 2, the third resin layer includes a first layer containing a polyamide resin as a main component and a second layer containing an ethylene-vinyl acetate copolymer saponified resin as a main component. The film for deep drawing. The film for deep drawing molding according to any one of claims 1 to 3, wherein an adhesive resin layer containing a polyolefin-based adhesive resin is provided between the second resin layer and the third resin layer. .. The film for deep drawing molding according to any one of claims 1 to 4, wherein an adhesive resin layer containing a polyolefin-based adhesive resin is provided between the third resin layer and the fourth resin layer. .. The film for deep drawing according to any one of claims 1 to 5, wherein the fourth resin layer has an easy peel strength of 0.8 N / 15 mm width or more and 4.0 N / 15 mm width or less. Any of claims 1 to 6, wherein the heat-resistant polyester resin has a glass transition point (Tg) of 130 ° C. or lower and an ultimate viscosity (IV) of 0.4 dl / g or more and 1.0 dl / g or less. The film for deep drawing molding according to item 1. The film for deep drawing molding according to any one of claims 1 to 7, wherein the thickness ratio of the first resin layer to the second resin layer is 1% or more and 15% or less. A deep-drawing package comprising the film for deep-drawing molding according to any one of claims 1 to 8. The deep-drawn package according to claim 9 , which is for food packaging.

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