JP7283620B2 - laminate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyester sealant excellent in heat-sealing strength and a package using the same, and more particularly to a polyester sealant suitable for laminating gas barrier layers.

Laminated films obtained by heat-sealing or laminating a sealant film have conventionally been used as packaging materials such as packages and lids for many distribution goods represented by foods, pharmaceuticals, and industrial products. The innermost surface (the surface in contact with the contents) of the packaging material is provided with a sealant layer made of polyolefin resin such as polyethylene or polypropylene, or copolymer resin such as ionomer or EMMA, which exhibits high sealing strength. It is known that these resins can achieve high adhesion strength by heat sealing.

However, the unstretched sealant film made of polyolefin resin as described in Patent Document 1 easily adsorbs components made of organic compounds such as oils and fats and perfumes, so it is said that the smell and taste of the contents are likely to change. have shortcomings. Therefore, in many cases, it is not suitable to use a sealant layer made of polyolefin resin as the innermost layer for packaging chemical products, pharmaceuticals, foods, and the like.

On the other hand, sealants made of acrylonitrile-based resins, such as those described in Patent Document 2, are less likely to adsorb organic compounds contained in chemical products, pharmaceuticals, foods, etc., and are therefore suitable for use as the innermost layer of packaging materials. there is However, acrylonitrile-based films have a problem of low heat seal strength in a low temperature range (150° C. or lower). In the bag-making process, when the heat sealing temperature becomes high, the maintenance frequency of the seal bar increases, which is not preferable from the viewpoint of productivity. Further, in order to improve the yield of bag making, the speed of the bag making line is increasing, and it is preferable that the sealing temperature is low in response to this requirement as well. Sealants made from acrylonitrile-based resins cannot satisfy these requirements.

In view of such problems, Patent Document 3 discloses a polyester-based sealant having non-adsorption of organic compounds and low-temperature sealing properties. However, the sealant described in Patent Literature 3 has the problem that the sealant not only shrinks due to heat during heat sealing, but also melts to form holes. For example, when a package using a sealant is produced, heat shrinkage of the sealant not only causes the shape of the bag to be lost, but also causes holes in the bag, which is not preferable because the bag cannot function as a storage bag. Thus, the sealant of Patent Document 3 has room for improvement in heat resistance.

Therefore, Patent Document 4 discloses a sealant with improved heat resistance. The sealant described in Patent Document 4 satisfies heat sealability and heat resistance by separating a layer having heat sealability from other layers and separately controlling the raw material compositions of these layers. However, since the sealant described in Patent Document 4 does not have the ability to block gases such as oxygen and water vapor (gas barrier properties), there is a problem that the shelf life of the contents is short.

Conventionally, as a measure for improving the gas barrier property of a film, it is well known to provide a gas barrier layer composed of an inorganic thin film by vapor deposition. When the gas barrier layer is provided, a so-called roll-to-roll system is employed in which a film that serves as a substrate is unwound from a film roll and conveyed via a metal roll. This system is preferably adopted because the substrate film passes through each process such as the vapor deposition process while continuously flowing, resulting in good productivity. However, in the roll-to-roll method, it is necessary to apply a constant tension so that the film does not sag between the metal rolls, and deformation (elongation) of the film due to this tension often poses a problem. A non-stretched film such as that described in Patent Document 1 has a large elongation due to tension, and therefore cracks easily occur even if a gas barrier layer is provided.

In addition, since the film is usually heated to a glass transition temperature (Tg) or higher in the vapor deposition process, the gas barrier layer tends to crack when the film is thermally shrunk. For example, Patent Document 5 discloses a laminate in which an inorganic thin film layer is provided on a sealant made of a polyester material to improve gas barrier properties. However, the laminate in which the gas barrier layer is formed using the polyester-based sealant described in Patent Document 5 does not exhibit gas barrier properties commensurate with the constituent materials and layer thickness of the gas barrier layer. The present inventors have found that this is because thermal shrinkage occurs when the film is heated in the vapor deposition process, cracks occur in the gas barrier layer, and the gas barrier properties deteriorate. In recent years, as the production speed has increased, the temperature of the film tends to be kept above Tg even after the film has left the vapor deposition process (cooling speed is slow). The problem of large defects (cracks) occurring in layers frequently occurs.
Furthermore, the present inventors have also found that the deformation behavior of the film reduces the gas barrier properties even after exiting the vapor deposition process. That is, the film shrinks when it is cooled after being heated and thermally expanded in the vapor deposition process, so that the gas barrier layer is likely to crack and the gas barrier property is lowered.

Japanese Patent No. 3817846 JP-A-7-132946 International Publication No. 2014-175313 JP 2017-165059 A JP 2017-165060 A

An object of the present invention is to solve the problems of the prior art as described above. That is, the object of the present invention is to have a low adsorption of the components of the contents, a high heat seal strength in a low temperature range, and an excellent gas barrier property without lowering the gas barrier property in a process such as a vapor deposition step for providing a gas barrier layer. To provide a polyester-based sealant film used for laminating a gas barrier layer, which can have

The present invention consists of the following configurations.
1. It has at least one layer each of a heat-sealing layer and a heat-resistant layer, and each layer is formed of polyester containing ethylene terephthalate as a main component, and is characterized by satisfying the following requirements (1) to (3). A polyester sealant film used for laminating a gas barrier layer.
(1) The seal strength when the heat seal layers are sealed at 140 ° C., 0.2 MPa, 2 seconds is 8 N / 15 mm or more and 30 N / 15 mm or less (2) Tension per unit cross-sectional area by thermomechanical analysis (TMA) The deformation rate in the longitudinal direction is 0% or more and 10% or less when the temperature is increased from 30°C to 140°C at 10°C/min while applying 1.7 N/mm2 (3) Thermomechanical analysis (TMA), unit While applying a tension per cross-sectional area of 1.7 N/mm2, the temperature was raised from 30°C to 160°C at a rate of 10°C/min, held at 160°C for 1 minute, and then cooled from 160°C to 30°C at a rate of 10°C/min. When the deformation rate in the longitudinal direction is -2% or more and 0% or less (negative value indicates shrinkage)
2. Any of neopentyl glycol, 1,4-cyclohexanedimethanol, 1,4-butanediol, and diethylene glycol as a diol monomer component other than ethylene glycol as a component constituting each polyester constituting the heat-sealing layer and the heat-resistant layer. or one or more, or containing isophthalic acid as an acid component other than terephthalic acid. The polyester sealant film according to .
3. A diol monomer component other than ethylene glycol is contained in all the monomer components of each polyester component constituting the heat-sealing layer and the heat-resistant layer, and the content of the diol monomer component satisfies the following (1) to (3). 1. or 2. The polyester sealant film according to .
(1) 30 mol% or more and 50 mol% or less in the heat seal layer (2) 9 mol% or more and 20 mol% or less in the heat-resistant layer (3) The content difference between the heat seal layer and the heat-resistant layer is 20 mol% or more and 35 4. mol % or less; 1. The gas barrier layer is an inorganic thin film layer. ~3. The polyester sealant film according to any one of 1.
5. 1 above. ~ 4. A laminate comprising at least one layer of the polyester sealant according to any one of .
6. 1 above. ~ 5. A package characterized by using at least a part of the polyester sealant according to any one of the above.
7. 5 above. 3. A package comprising at least a part of the laminate according to 1.

The polyester-based sealant film of the present invention has little adsorption of components of the content, has high heat seal strength in a low temperature range, and has excellent gas barrier properties when provided with a gas barrier layer.

It is a diagram obtained by thermomechanical analysis (TMA) to determine the deformation rate when tension is applied.

The present invention has at least one layer each of a heat-sealing layer and a heat-resistant layer, and each layer is formed of polyester containing ethylene terephthalate as a main constituent, and the following requirements (1) to (3) are satisfied. It is a polyester-based sealant film used for laminating a gas barrier layer, characterized by filling.
(1) The seal strength when the heat seal layers are sealed at 140 ° C., 0.2 MPa, 2 seconds is 8 N / 15 mm or more and 30 N / 15 mm or less (2) Tension per unit cross-sectional area by thermomechanical analysis (TMA) The deformation rate in the longitudinal direction is 0% or more and 10% or less when the temperature is increased from 30°C to 140°C at 10°C/min while applying 1.7 N/mm2 (3) Thermomechanical analysis (TMA), unit While applying a tension per cross-sectional area of 1.7 N/mm2, the temperature was raised from 30°C to 160°C at a rate of 10°C/min, held at 160°C for 1 minute, and then cooled from 160°C to 30°C at a rate of 10°C/min. When the deformation rate in the longitudinal direction is -2% or more and 0% or less (negative value indicates shrinkage)
Hereinafter, the polyester sealant used for laminating the gas barrier layer of the present invention will be described.

1. Properties of sealants 1.1. Heat Seal Strength The polyester sealant film (hereinafter sometimes simply referred to as "sealant") used for laminating the gas barrier layer of the present invention was prepared at a temperature of 140°C, a seal bar pressure of 0.2 MPa, and a sealing time of 2 seconds. It is preferable that the heat seal strength when heat-sealed with is 8 N/15 mm or more and 30 N/15 mm or less. In addition, when the sealant is divided into layers having a plurality of functions, it is necessary to bring the seal layers into contact with each other when measuring the heat seal strength. The layer structure of the sealant of the present invention will be described later.
If the heat seal strength is less than 8 N/15 mm, the sealed portion is easily peeled off and cannot be used as a packaging bag. The heat seal strength is preferably 9 N/15 mm or more, more preferably 10 N/15 mm or more. It is preferable that the heat seal strength is high, but the upper limit that can be obtained at present is about 30 N/15 mm. It can be said that even 29 N/15 mm is sufficiently preferable for practical use.

1.2. Heat deformation rate when tension is applied The sealant of the present invention is heated from 30 ° C. to 140 ° C. at 10 ° C./min while applying a tension of 1.7 N / mm ² per unit cross-sectional area (width x thickness) in the longitudinal direction. It is preferable that the deformation ratio is 0% or more and 10% or less. Longitudinal heat distortion is measured using thermomechanical analysis (TMA). A detailed measurement method is described in Examples. The longitudinal direction refers to the film-forming direction in the production of the sealant film, and is synonymous with the longitudinal direction and the MD direction, which will be described later.
If the heat distortion rate in the longitudinal direction exceeds 10%, it means that the sealant tends to stretch in the vapor deposition process, and cracks tend to occur in the vapor-deposited gas barrier film, which is not preferable. The heat deformation rate in the longitudinal direction is more preferably 9% or less, more preferably 8% or less. The closer the heat deformation ratio in the longitudinal direction is to 0%, the more difficult it is for the sealant to deform. It is not preferable because In the present invention, the lower limit of the heat distortion rate in the longitudinal direction is 0%, and even 1% is practically preferable enough.

1.3. Cooling deformation rate when tension is applied The sealant of the present invention is heated from 30 ° C. to 160 ° C. at 10 ° C./min while applying a tension of 1.7 N / mm ² per unit cross-sectional area (width x thickness) in the longitudinal direction. After holding at 160 ° C. for 1 minute, the deformation rate when cooling from 160 ° C. to 30 ° C. at 10 ° C./min is -2% or more and 0% or less (negative value indicates shrinkage) preferable. Longitudinal cooling deformation is measured using thermomechanical analysis (TMA). A detailed measurement method is described in Examples.
If the cooling deformation rate in the longitudinal direction is less than -2%, it means that the sealant tends to shrink after leaving the vapor deposition process, and cracks tend to occur in the vapor-deposited gas barrier film, which is not preferable. The cooling deformation rate in the longitudinal direction is more preferably −1.8% or more, more preferably −1.6% or more. The closer the longitudinal cooling deformation rate is to 0%, the more difficult it is for the sealant to deform. I don't like it because In the present invention, the upper limit is 0% because only shrinkage occurs during cooling. Even if the upper limit of the cooling deformation rate in the longitudinal direction is -0.2%, it can be said that it is sufficiently preferable for practical use.

1.4. Hot water heat shrinkage The sealant of the present invention preferably has a hot water heat shrinkage of −5% or more and 5% or less in both the width direction and the longitudinal direction when treated in hot water at 98° C. for 10 seconds. If the shrinkage ratio exceeds 5%, the shrinkage in a high-temperature environment increases and the original shape cannot be maintained. The hot water heat shrinkage rate is more preferably 4% or less, and even more preferably 3% or less. On the other hand, if the hot water heat shrinkage ratio is less than 0%, it means that the sealant is stretched, and it is not preferable because it becomes difficult for the film to maintain its original shape as in the case where the shrinkage ratio is high.

1.5. Haze The sealant of the present invention preferably has a haze of 1% or more and 15% or less. If the haze exceeds 15%, the transparency of the film is deteriorated, and the visibility of the contents is deteriorated when the film is used as a package such as a bag. The upper limit of haze is more preferably 13% or less, particularly preferably 11% or less. The lower the haze, the higher the transparency, which is preferable. However, in the current state of the art, 1% is the lower limit, and 2% or more is practically sufficient.

1.6. Thickness The thickness of the sealant of the present invention is not particularly limited, but is preferably 3 μm or more and 200 μm or less. If the thickness of the film is less than 3 μm, the heat seal strength may be insufficient and processing such as printing may become difficult, which is not so preferable. Although the thickness of the film may be thicker than 200 μm, the weight of the film used increases and the chemical cost increases, which is not preferable. The thickness of the film is more preferably 5 μm or more and 160 μm or less, and even more preferably 7 μm or more and 120 μm or less.

1.7. Types of Contents and Adsorption Amount The sealant of the present invention is characterized by being less likely to adsorb organic compounds contained in chemical products, pharmaceuticals, foods, and the like. Examples of the organic compounds include d-limonene, citral, citronellal, p-menthane, pinene, terpinene, myrcene, carene, geraniol, nerol, citronellal, terpineol, l-menthol, nerolidol, borneol, dl-camphor, lycopene. , carotene, trans-2-hexenal, cis-3-hexenol, β-ionone, selinen, 1-octen-3-ol, benzyl alcohol, octal tulobuterol hydrochloride, and tocopherol acetate. .
The amount of adsorption to the sealant varies depending on the adsorption conditions (concentration of adsorbate, storage period, temperature, etc.), but the amount of adsorption when stored for one week by the method shown in the examples below is 0 μg/cm ² or more and 2 μg/cm. ² is preferred. An adsorption amount of 0 μg/cm ² indicates that the contents are not adsorbed to the sealant at all. The adsorption amount is more preferably 1.8 μg/cm ² or less, and even more preferably 1.6 μg/cm ² or less.

Since the sealant of the present invention has a heat-sealable layer made of a polyester-based component, there is a possibility that the adsorption of organic compounds having a similar chemical structure may increase. Specifically, since the polyester-based component that constitutes the sealant has four oxygen atoms, as the chemical structure of the organic compound, the greater the number of oxygen atoms (closer to four), the greater the solubility of the organic compound in the sealant. Adsorptivity tends to increase with For example, packaging a content containing eugenol with two oxygen atoms or methyl salicylate with three oxygen atoms is not preferable because the adsorption amount tends to exceed 2 μg/cm ² .

2. Layer Configuration and Layer Ratio of Sealant The sealant of the present invention has at least one layer each of a heat-sealing layer and a heat-resistant layer. Considering that a heated seal bar (heat jaw) or the like is used for heat-sealing, the sealant of the present invention has a seal layer and a heat-resistant layer in order to achieve both heat-sealability and heat resistance. A two-kind two-layer structure having one layer each is preferable. Constituent requirements for each layer will be described later, but the layer with the highest ethylene terephthalate component content is the heat-resistant layer. The layer structure of the sealant may have a third layer other than the sealing layer and the heat-resistant layer, but the sealing layer must be positioned as the outermost layer of one of them.
The ratio of the seal layer to the total thickness of the sealant is preferably 20% or more and 80% or less. If the layer ratio of the heat-sealing layer is less than 20%, the heat-sealing strength of the sealant is lowered, which is not preferable. If the layer ratio of the seal layer exceeds 80%, the heat seal strength of the sealant is improved, but the heat resistance is lowered, which is not preferable. The layer ratio of the heat seal layer is more preferably 30% or more and 70% or less.
In addition, the outermost layer (including the seal layer) of the sealant of the present invention can be provided with a layer that has been subjected to corona treatment, coating treatment, flame treatment, etc. in order to improve the printability and slipperiness of the film surface. and can be provided arbitrarily within the scope of the requirements of the present invention.

3. Constituent Raw Materials of Sealant Hereinafter, description will be made assuming a two-kind two-layer structure composed of a sealing layer and a heat-resistant layer, which is a preferred embodiment of the present invention.

3.1. Type of Polyester Raw Material The type of polyester raw material that constitutes the sealant of the present invention is one that contains an ethylene terephthalate unit as a main component. Here, "contained as a main component" means to contain 50 mol% or more when the total amount of the components is 100 mol%. Since the ethylene terephthalate unit contains a benzene ring derived from a carboxylic acid, the rigidity of the molecule is improved, and as a result, the cooling deformation rate upon application of tension can easily approach 0%.
Moreover, it is preferable that the polyester used in the polyester-based resin layer of the present invention contains at least one component other than ethylene terephthalate. This is because the presence of components other than ethylene terephthalate improves the heat seal strength of the seal layer. In the heat-resistant layer, it is preferable that the amount of components other than ethylene terephthalate is small. be. The content of each component differs between the sealing layer and the heat-resistant layer, and will be described later.
Examples of dicarboxylic acid monomers that can be components other than terephthalic acid constituting ethylene terephthalate include aromatic dicarboxylic acids such as isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and orthophthalic acid, adipic acid, Aliphatic dicarboxylic acids such as azelaic acid, sebacic acid, decanedicarboxylic acid, and alicyclic dicarboxylic acids are included. However, it is preferable not to include polyvalent carboxylic acids having a valence of 3 or higher (eg, trimellitic acid, pyromellitic acid, anhydrides thereof, etc.) in the polyester. Among the above carboxylic acid components, isophthalic acid is preferably used because the heat seal strength between the heat seal layers can be easily adjusted to 8 N/15 mm or more.

Examples of diol monomers that can be components other than ethylene glycol constituting ethylene terephthalate include neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol, 2,2-diethyl 1,3-propanediol, 2-n- Butyl-2-ethyl-1,3-propanediol, 2,2-isopropyl-1,3-propanediol, 2,2-di-n-butyl-1,3-propanediol, hexanediol, 1,4- Examples include long-chain diols such as butanediol, aliphatic diols such as hexanediol, and aromatic diols such as bisphenol A. However, the polyester should not contain a diol having 8 or more carbon atoms (e.g., octanediol, etc.) or a trihydric or higher polyhydric alcohol (e.g., trimethylolpropane, trimethylolethane, glycerin, diglycerin, etc.). preferable.
Furthermore, polyester elastomers containing ε-caprolactone, tetramethylene glycol, etc. may be included as components constituting the polyester. The polyester elastomer has the effect of lowering the melting point of the polyester-based resin layer, so it can be suitably used particularly for the heat seal layer.

Among these, by using one or more of neopentyl glycol, 1,4-cyclohexanedimethanol, 1,4-butanediol, and diethylene glycol, the heat seal strength between the heat seal layers can easily be 8 N / 15 mm or more. It is preferable because It is more preferable to use one or more of neopentyl glycol and 1,4-cyclohexanedimethanol, and it is particularly preferable to use neopentyl glycol.

In the polyester resin layer constituting the sealant of the present invention, various additives such as waxes, antioxidants, antistatic agents, crystal nucleating agents, viscosity reducing agents, heat stabilizers, A coloring pigment, an anti-coloring agent, an ultraviolet absorber, and the like can be added. Further, it is preferable to add fine particles as a lubricant for improving the slipperiness of the film at least to the outermost layer of the film. Any fine particles can be selected. Examples of inorganic fine particles include silica, alumina, titanium dioxide, calcium carbonate, kaolin, and barium sulfate. Organic fine particles include acrylic resin particles, melamine resin particles, silicone resin particles, and crosslinked polystyrene. Particles and the like can be mentioned. The average particle size of the fine particles can be appropriately selected within the range of 0.05 to 3.0 μm as measured by a Coulter counter.
As a method of blending the particles into the polyester resin layer constituting the sealant of the present invention, for example, it can be added at any stage in the production of the polyester resin (resin). After completion of the exchange reaction, it is preferable to add the polycondensation reaction as a slurry dispersed in ethylene glycol before starting the polycondensation reaction to proceed with the polycondensation reaction. In addition, a method of blending a polyester resin raw material with a slurry of particles dispersed in ethylene glycol, water, or other solvents using a kneading extruder with a vent, or a method of kneading and extruding dried particles and a polyester resin raw material. A method of blending using a machine is also included.

3.2. Component Amount of Polyester Raw Material Contained in Sealing Layer In the polyester used for the sealing layer, the content of dicarboxylic acid monomer and/or diol monomer, which are components other than terephthalic acid and ethylene glycol constituting ethylene terephthalate, is 30 mol % or more. is preferred, 32 mol % or more is more preferred, and 34 mol % or more is particularly preferred. Further, the upper limit of the content of monomers other than ethylene terephthalate is 50 mol %.
If the amount of the monomer other than ethylene terephthalate contained in the seal layer is less than 30 mol %, even if the molten resin is rapidly solidified after being extruded from the die, it will crystallize in the subsequent stretching and heat setting steps. , it is difficult to obtain a heat seal strength of 8 N/15 mm or more, which is not preferable.
On the other hand, when the amount of the monomer other than the ethylene terephthalate contained in the seal layer is 50 mol% or more, the heat seal strength of the film can be increased, but the heat resistance of the seal layer is extremely low. When heat-sealing, the periphery of the seal portion is blocked (a phenomenon in which heat conduction from the heating member results in sealing in a wider area than intended), making proper heat-sealing difficult. The content of monomers other than ethylene terephthalate is more preferably 48 mol % or less, particularly preferably 46 mol % or less.

3.3. Component amount of polyester raw material contained in the heat-resistant layer The polyester used for the heat-resistant layer has a content of dicarboxylic acid monomers and/or diol monomers that are components other than terephthalic acid and ethylene glycol that constitute ethylene terephthalate is 9 mol% or more. is preferred, 10 mol % or more is more preferred, and 11 mol % or more is particularly preferred. Further, the upper limit of the content of monomers other than ethylene terephthalate is 20 mol %.
If the amount of the monomer other than the ethylene terephthalate contained in the heat-resistant layer is less than 9 mol %, the difference in heat shrinkage from the seal layer increases, and the curl of the sealant increases, which is not preferable. If the difference in the content of the monomers other than the ethylene terephthalate contained in the heat-resistant layer and the seal layer increases, the difference in thermal shrinkage between the layers during heat setting increases, even if the cooling after heat setting is strengthened. However, the shrinkage toward the seal layer side becomes large, and the curl becomes large.
On the other hand, when the amount of the monomer other than the ethylene terephthalate contained in the heat-resistant layer is 20 mol% or more, the heat resistance of the sealant is lowered such that the heat applied during heat-sealing causes holes. I don't like it because The content of monomers other than ethylene terephthalate is more preferably 19 mol % or less, particularly preferably 18 mol % or less.
Further, the content of monomers other than ethylene terephthalate for controlling curling should be such that the difference between the seal layer and the heat-resistant layer is 10 mol % or more and 45 mol % or less, in addition to the amount of each layer alone. It is more preferable if there is, and more preferably 11 mol % or more and 44 mol % or less.

4. Manufacturing conditions of sealant 4.1. Melt Extrusion The sealant of the present invention is prepared according to the above 3.1. It can be obtained by melt-extruding the polyester raw material described in "Raw Material Species of Polyester-Based Resin Layer" with an extruder to form an unstretched film, and stretching it by a predetermined method shown below. When the sealant includes a seal layer, a heat-resistant layer, or other layers, the layers may be laminated before or after stretching. When the layers are laminated before being stretched, it is preferable to adopt a method in which the raw material resins for each layer are melt-extruded by separate extruders and joined using a feed block or the like in the middle of the resin flow path. In the case of lamination after stretching, it is preferable to employ lamination in which separately formed films are bonded together with an adhesive, or extrusion lamination in which a melted polyester resin is poured onto the surface layer of a single or laminated film to laminate. Among these, the method of laminating each layer before stretching is preferable.
As described above, the polyester resin can be obtained by polycondensation by selecting the types and amounts of the dicarboxylic acid component and the diol component so as to contain an appropriate amount of a monomer that can be a component other than ethylene terephthalate. Moreover, two or more kinds of chip-like polyesters can be mixed and used as a raw material for the polyester-based resin layer.

When the raw material resin is melt-extruded, it is preferable to dry the polyester raw material for each layer using a dryer such as a hopper dryer, a paddle dryer, or a vacuum dryer. After drying the polyester raw material for each layer, it is melted at a temperature of 200 to 300° C. using an extruder and extruded as a laminated film. Any existing method such as a T-die method, a tubular method, or the like can be employed for the extrusion.
Thereafter, by rapidly cooling the film melted by extrusion, an unstretched film can be obtained. As a method for rapidly cooling the molten resin, a method of obtaining a substantially non-oriented resin sheet by casting the molten resin from a die onto a rotating drum and rapidly cooling and solidifying the resin can be suitably employed.

The film may be formed by any method of non-stretching, uniaxial stretching (stretching in at least one of the vertical (longitudinal) direction and horizontal (width) direction), and biaxial stretching. From the viewpoint of mechanical strength and productivity of the laminate of the present invention, uniaxial stretching is preferable, and biaxial stretching is more preferable. In the following, the description will focus on the sequential biaxial stretching method by longitudinal stretching and then transverse stretching, in which the longitudinal stretching is performed first, and then the transverse stretching. It does not matter because only the main orientation direction is changed. A simultaneous biaxial stretching method in which the film is stretched in the machine direction and the transverse direction at the same time may also be used.

4.2. First (Longitudinal) Stretching For stretching in the first direction (longitudinal or longitudinal direction), the unstretched film is preferably introduced into a longitudinal stretching machine in which a plurality of roll groups are continuously arranged. In longitudinal stretching, it is preferable to preheat the film with preheating rolls until the film temperature reaches 65°C to 90°C. If the film temperature is lower than 65° C., it becomes difficult to stretch the film in the longitudinal direction, and the film tends to break, which is not preferable. On the other hand, if the temperature is higher than 90° C., the film tends to stick to the roll, and the film tends to wind around the roll or stain the roll during continuous production, which is not preferable.
When the film temperature reaches 65°C to 90°C, it is longitudinally stretched. The longitudinal draw ratio is preferably 1-fold or more and 5-fold or less. Since 1 time means no longitudinal stretching, the longitudinal stretching ratio is 1 time to obtain a transversely uniaxially stretched film, and the longitudinal stretching ratio is 1.1 times or more to obtain a biaxially stretched film. By setting the longitudinal draw ratio to 1.1 times or more, the mechanical strength can be increased by imparting molecular orientation to the longitudinal direction of the film, so that the heat deformation ratio during application of tension can be easily reduced to 10% or less. Furthermore, by giving the film molecular orientation in the longitudinal direction by setting the longitudinal draw ratio to 1.1 times or more, the cooling deformation ratio during application of tension can be easily brought close to 0%. The upper limit of the draw ratio in the longitudinal direction may be any number, but if the draw ratio in the longitudinal direction is too high, it becomes difficult to draw in the transverse direction and the film tends to break, so it is preferably 5 times or less.

4.3. Intermediate Heat Treatment After the first (longitudinal) stretching, it is preferable to include a step of heating the film (intermediate heat treatment) in order to reduce the shrinkage of the film caused by the stretching. At the time of this intermediate heat treatment, fixed-length heating in which the film is heated while maintaining the length of the film constant, or relaxation treatment in which the film is heated while being relaxed in the longitudinal direction, or the like can be employed. Among these, in order to reduce the shrinkage rate in the longitudinal direction of the film caused by longitudinal stretching, it is a preferred embodiment to adopt relaxation treatment.

Relaxation in the longitudinal direction can reduce not only the shrinkage rate in the longitudinal direction of the film, but also the bowing phenomenon (distortion) occurring in the tenter. This is because in the second (horizontal) stretching and final heat treatment in the post-process, the film is heated while both ends in the width direction are held, so that only the central portion of the film shrinks in the longitudinal direction. The relaxation rate in the longitudinal direction is preferably 0% or more and 70% or less (0% relaxation rate means no relaxation). Since the upper limit of the rate of relaxation in the longitudinal direction is determined by the raw materials used and conditions for longitudinal stretching, the relaxation cannot be performed beyond this limit. In the polyester sealant of the present invention, the upper limit of the relaxation rate in the longitudinal direction is 70%. To relax in the longitudinal direction, heat the film after longitudinal stretching at a temperature of 65 ° C. to 100 ° C. or less, adjust the speed difference of the rolls (lower the roll speed on the downstream side), or shorten the distance between clips ( can be implemented by slowing down the moving speed on the downstream side). Any of rolls, near-infrared rays, far-infrared rays, hot air heaters, etc. can be used as the heating means. In addition, relaxation in the longitudinal direction can be performed by narrowing the clip spacing in the longitudinal direction not only immediately after longitudinal stretching, but also in transverse stretching (including a preheating zone) or final heat treatment (in this case, both ends of the film in the width direction are relaxed in the longitudinal direction, bowing distortion is reduced), and can be performed at any time.
After relaxing in the longitudinal direction (longitudinal stretching if relaxation is not performed), the film is preferably cooled once, preferably with cooling rolls having a surface temperature of 20 to 40°C.

4.4. Second (horizontal) stretching After the first (longitudinal) stretching, the film is stretched at 65°C to 110°C for 3 to 5 minutes while both ends of the film in the width direction (perpendicular to the longitudinal direction) are held with clips in the tenter. It is preferable to perform lateral stretching at a draw ratio of about 100%. Preheating is preferably performed before stretching in the transverse direction, and the preheating is preferably performed until the film surface temperature reaches 75°C to 120°C.
After transverse stretching, the film is preferably passed through an intermediate zone in which no active heating operation is performed. Since the temperature in the final heat treatment zone is higher than that in the transverse stretching zone of the tenter, the heat (hot air itself or radiant heat) in the final heat treatment zone flows into the transverse stretching process unless an intermediate zone is provided. In this case, since the temperature of the lateral stretching zone is not stable, not only is the accuracy of the thickness of the film deteriorated, but also the physical properties such as the heat seal strength and the heat shrinkage are varied. Therefore, it is preferable that the transversely stretched film is passed through an intermediate zone for a predetermined period of time, and then subjected to final heat treatment. In this intermediate zone, when a strip of paper is hung without the film passing through it, the accompanying flow accompanying the running of the film, the transverse stretching zone, and the final It is important to block hot air from the heat treatment zone. About 1 to 5 seconds is sufficient for passing through the intermediate zone. If it is shorter than 1 second, the length of the intermediate zone will be insufficient and the heat shielding effect will be insufficient. On the other hand, it is preferable that the intermediate zone is long.

4.5. Final Heat Treatment After passing through the intermediate zone, heat treatment is preferably performed at 160° C. or higher and 250° C. or lower in the final heat treatment zone. If the final heat treatment temperature is less than 160 ° C., the heat deformation rate when tension is applied when used as a sealant is less than 0% (shrinks), and the shrinkage rate in hot water at 98 ° C. is higher than 5%. I don't like it because The higher the final heat treatment temperature, the more difficult it is for the heat deformation rate of the film to fall below 0% when tension is applied, and the 98°C hot water shrinkage rate decreases. , the film may melt and drop into the tenter during the final heat treatment step, which is not preferable.
At the time of the final heat treatment, shrinkage in the width direction can be reduced by reducing the distance between the clips of the tenter by an arbitrary ratio (relaxation in the width direction). Therefore, in the final heat treatment, it is preferable to perform relaxation in the width direction within a range of 0% or more and 10% or less (a relaxation rate of 0% indicates that no relaxation is performed). The higher the relaxation ratio in the width direction, the lower the shrinkage ratio in the width direction. , so relaxation cannot be performed beyond this. In the sealant of the present invention, the upper limit of the relaxation rate in the width direction is 10%. Moreover, during the final heat treatment, as described above, the distance between the clips of the tenter can be shortened by an arbitrary ratio in the longitudinal direction (relaxation in the longitudinal direction).
The passing time through the final heat treatment zone is preferably 2 seconds or more and 20 seconds or less. If the passage time is less than 2 seconds, the film passes through the heat treatment zone before the surface temperature reaches the set temperature, and the heat treatment is meaningless. The longer the passing time, the more effective the heat treatment. Therefore, the passing time is preferably 2 seconds or longer, more preferably 5 seconds or longer. However, if the transit time is increased, the equipment will become huge, so 20 seconds or less is practically sufficient.

4.6. Cooling After passing through the final heat treatment zone, it is preferable to cool the film with cooling air at 10°C or higher and 30°C or lower in the cooling zone. At this time, the cooling efficiency is improved by decreasing the temperature of the cooling air or increasing the air velocity so that the actual temperature of the film at the exit of the tenter becomes lower than the glass transition temperature of the sealing layer or the heat-resistant layer, whichever is lower. is preferred. The actual temperature is the film surface temperature measured with a non-contact radiation thermometer. If the actual temperature of the film at the exit of the tenter exceeds the glass transition temperature, the film will thermally shrink when both ends of the film held by the clips are released. At this time, the film curls into a seal layer having a large heat shrinkage, which is not preferable.
The passing time through the cooling zone is preferably 2 seconds or more and 20 seconds or less. If the passing time is 2 seconds or less, the film passes through the cooling zone before the surface temperature reaches the glass transition temperature, resulting in large curls. The longer the passing time, the higher the cooling effect. Therefore, it is preferably 2 seconds or longer, more preferably 5 seconds or longer. However, if the transit time is increased, the equipment will become huge, so 20 seconds or less is practically sufficient.
After that, the film roll is obtained by winding the film while cutting and removing both ends of the film.

5. Gas Barrier Layer Since the sealant of the present invention is premised on providing a gas barrier layer mainly composed of an inorganic thin film, it is preferable to provide a gas barrier layer. In the following description, the sealant of the present invention provided with a gas barrier layer is simply referred to as a "laminate" or "gas barrier layer laminate".

5.1. Characteristics of gas barrier layer laminate 5.1.1. Water vapor transmission rate The laminate using the sealant of the present invention has a water vapor transmission rate of 0.05 [g/(m ² ·d)] or more and 4 g/m ² or less in an environment with a temperature of 40 ° C. and a relative humidity of 90% RH. is preferable. If the water vapor transmission rate exceeds 4 [g/(m ² ·d)], the shelf life of the contents will be shortened when used as a bag containing the contents, which is not preferable. On the other hand, when the water vapor permeability is less than 0.05 [g/(m ² ·d)], the gas barrier property is enhanced and the shelf life of the contents is increased, which is preferable, but the current technical level is 0.05 [g /(m ² ·d)] is the lower limit. Even if the lower limit of the water vapor permeability is 0.05 [g/(m ² ·d)], it can be said that it is practically sufficient. The upper limit of the water vapor permeability is preferably 3.8 [g/(m ² ·d)], more preferably 3.6 [g/(m ² ·d)].

5.1.2. Oxygen Permeability A laminate using the sealant of the present invention has an oxygen permeability of 0.05 [cc/(m ² · d · atm)] or more in an environment with a temperature of 23 ° C. and a relative humidity of 65% RH. /(m ² ·d·atm)] or less. If the oxygen permeability exceeds 4 [cc/(m ² ·d·atm)], the shelf life of the contents will be shortened, which is not preferable. On the other hand, when the oxygen permeability is less than 0.05 [cc/(m ² ·d · atm)], the gas barrier property is enhanced and the shelf life of the contents is increased, which is preferable, but the current technical level is oxygen permeability is 0.05 [cc/(m ² ·d·atm)]. Even if the lower limit of the oxygen permeability is 0.05 [cc/(m ² ·d·atm)], it can be said to be practically sufficient. The upper limit of the oxygen permeability is preferably 3.8 [cc/(m ² ·d·atm)], more preferably 3.6 [cc/(m ² ·d·atm)].

5.2. Gas barrier layer raw material species and composition The raw material species of the gas barrier layer is not particularly limited, conventionally known materials can be used, and can be appropriately selected according to the purpose in order to satisfy the desired gas barrier properties. Examples of raw material species for the gas barrier layer include metals such as silicon, aluminum, tin, zinc, iron, and manganese, and inorganic compounds containing one or more of these metals. Applicable inorganic compounds include oxides and nitrides. , carbides, fluorides, and the like. These inorganic substances or inorganic compounds may be used singly or in combination. In particular, it is preferable to use silicon oxide (SiOx) or aluminum oxide (AlOx) singly (monoelement) or in combination (binary element) because the transparency of the sealant provided with the gas barrier layer can be improved. When the component of the inorganic compound consists of a binary of silicon oxide and aluminum oxide, the content of aluminum oxide is preferably 20% by mass or more and 80% by mass or less, more preferably 25% by mass or more and 70% by mass or less. . If the content of aluminum oxide is 20% by mass or less, the density of the gas barrier layer may decrease and the gas barrier properties may deteriorate, which is not preferable. On the other hand, if the content of aluminum oxide is 80% by mass or more, the flexibility of the gas barrier layer is lowered, cracks are likely to occur, and as a result, the gas barrier properties may be lowered, which is not preferable.
If the oxygen/metal element ratio of the metal oxide used for the gas barrier layer is 1.3 or more and less than 1.8, the gas barrier properties are less varied, and excellent gas barrier properties are always obtained, which is preferable. The oxygen/metal element ratio can be obtained by measuring the amount of each element of oxygen and metal by X-ray photoelectron spectroscopy (XPS) and calculating the oxygen/metal element ratio.

5.3. Method for Forming Gas Barrier Layer The method for forming the gas barrier layer is not particularly limited, and known production methods can be employed as long as the object of the present invention is not impaired, but vapor deposition is preferably employed. For example, a vacuum deposition method, a sputtering method, a PVD method (physical vapor deposition method) such as ion blasting, or a CVD method (chemical vapor deposition method) can be used. A physical vapor deposition method is preferred, and a vacuum vapor deposition method is particularly preferred in terms of production speed and stability. As a heating method in the vacuum deposition method, resistance heating, high-frequency induction heating, electron beam heating, or the like can be used. As a reactive gas, oxygen, nitrogen, water vapor, or the like may be introduced, or reactive vapor deposition using means such as ozone addition or ion assist may be used. Also, the film forming conditions may be changed, such as applying a bias to the substrate, raising the substrate temperature, cooling the substrate, etc., as long as the object of the present invention is not compromised.
A method for forming a gas barrier layer by vacuum deposition will be described below. When forming the gas barrier layer, the sealant (film) of the present invention is conveyed to a gas barrier layer manufacturing apparatus via a metal roll. An example of the configuration of the gas barrier layer manufacturing apparatus includes an unwinding roll, a coating drum, a winding roll, an electron beam gun, a crucible, and a vacuum pump. The film is set on an unwinding roll, passes through a coating drum, and is wound up by a winding roll. The film pass line (inside the gas barrier layer manufacturing equipment) is evacuated by a vacuum pump, and the inorganic material set in the crucible is evaporated by the beam emitted from the electron gun and deposited onto the film passing through the coating drum. . During the deposition of the inorganic material, the film is subjected to heat and tension between the unwind and take-up rolls. If the temperature applied to the film is too high, not only will the heat shrinkage of the film increase, but the softening will proceed, so that elongation deformation due to tension will easily occur. Furthermore, the temperature drop (cooling) of the film after exiting the vapor deposition process becomes large, the amount of shrinkage after expansion (different from heat shrinkage) becomes large, and cracks occur in the gas barrier layer, making it difficult to achieve the desired gas barrier properties. It is not preferable because On the other hand, the lower the temperature applied to the film, the more preferable it is because the deformation of the film is suppressed. . The temperature applied to the film is preferably 100° C. or higher and 180° C. or lower, more preferably 110° C. or higher and 170° C. or lower, and even more preferably 120° C. or higher and 160° C. or lower. Also, if the tension applied to the film is too high, the film tends to be elongated and deformed, which is not preferable. On the other hand, if the tension applied to the film is too low, the heat shrinkage caused by heating the film cannot be suppressed, and the deformation also becomes large, which is not preferable. The tension per unit cross-sectional area (width x thickness) applied to the film is preferably 0.2 N/mm ² or more and 3 N/mm ² or less, and is 0.6 N/mm ² or more and 2.6 N/mm ² or less. More preferably, it is 1 N/mm ² or more and 2.2 N/mm ² or less.

6. Overcoat layer 6.1. Type of overcoat layer The sealant of the present invention is provided with an overcoat layer on top of the gas barrier layer mentioned in "5. Gas barrier layer" above for the purpose of improving scratch resistance and further gas barrier properties. can also The type of overcoat layer is not particularly limited, but conventionally used compositions such as a composition comprising a urethane resin and a silane coupling agent, a compound comprising an organosilicon and its hydrolyzate, a water-soluble polymer having a hydroxyl group or a carboxyl group, etc. A known material can be used, and it can be appropriately selected according to the purpose in order to satisfy the desired gas barrier property and the like.
In addition, one or more additives are added to the overcoat layer for the purpose of imparting antistatic properties, ultraviolet absorption properties, coloration, thermal stability, slipperiness, etc., to the extent that the objects of the present invention are not impaired. The type and amount of each additive can be appropriately selected according to the desired purpose.

6.2. Formation Method of Overcoat Layer When forming an overcoat layer, the sealant of the present invention or a laminate obtained by providing the sealant of the present invention with a gas barrier layer (hereinafter collectively referred to as a base film) is coated with a coating facility. to convey through metal rolls. Examples of equipment configuration include an unwinding roll, a coating process, a drying process, and a winding process. At the time of overcoating, the laminate set on the unwinding roll is passed through a metal roll through a coating process and a drying process, and finally led to a take-up roll. The coating method is not particularly limited, and gravure coating, reverse coating, dipping, low coating, air knife coating, comma coating, screen printing, spray coating, gravure offset, die coating, bar coating, etc. A conventionally known method can be employed, and can be appropriately selected according to the desired purpose. Among these, the gravure coating method, the reverse coating method, and the bar coating method are preferable from the viewpoint of productivity. As a drying method, one or a combination of two or more heating methods such as hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, and UV irradiation can be used.

In the drying process, the base film is heated and tension is also applied between metal rolls. If the temperature at which the base film is heated in the drying process is too high, not only will the heat shrinkage of the base film increase, but the softening will progress, making it easier for elongation deformation due to tension to occur. Cracks are likely to occur. Furthermore, after the laminate leaves the drying process, the temperature drop (cooling) of the laminate increases, and the amount of shrinkage after expansion (different from heat shrinkage) increases accordingly, causing cracks in the gas barrier layer and overcoat layer. It is not preferable because it becomes difficult to satisfy the desired gas barrier property. On the other hand, the lower the temperature at which the base film is heated, the more preferable it is because the deformation of the base film is suppressed. The temperature at which the substrate film is heated is preferably 60° C. or higher and 200° C. or lower, more preferably 80° C. or higher and 180° C. or lower, and even more preferably 100° C. or higher and 160° C. or lower. On the other hand, if the tension applied to the base film is too high, the base film tends to be elongated and deformed, which is not preferable. On the other hand, if the tension applied to the base film is too low, the heat shrinkage caused by the heating of the base film cannot be suppressed, and the deformation also becomes large, which is not preferable. The tension per unit cross-sectional area (width x thickness) applied to the base film is preferably 0.2 N/mm ² or more and 3 N/mm 2 or less, and 0.6 N/mm ^{2 or} more and 2.6 N/mm ² or less. It is more preferable if there is, and more preferable if it is 1 N/mm ² or more and 2.2 N/mm ² or less.

7. Structure of package, bag-making method The sealant having the above characteristics, the sealant provided with the gas barrier layer listed in "5. Gas barrier layer", and the sealant provided with the overcoat layer listed in "6. Overcoat layer" are It can be suitably used as a package. The sealant of the present invention can be bagged alone or laminated with other materials. Other layers constituting the sealant include, for example, a non-stretched film containing polyethylene terephthalate as a component, a non-stretched, uniaxially stretched or biaxially stretched film containing another amorphous polyester as a component, and nylon as a component. non-stretched, uniaxially-stretched or biaxially-stretched films containing polypropylene as a constituent component; The method of using the sealant in the package is not particularly limited, and conventionally known production methods such as the application forming method, the laminating method, and the heat sealing method can be employed.

Although at least a portion of the package may be composed of the sealant according to the present invention, a configuration in which the sealant described above is present in the entire package is preferable because the gas barrier properties of the package are improved. In addition, the sealant of the present invention may be applied to any layer of the package. is preferably the innermost layer.
There are no particular limitations on the method for making a package having the sealant of the present invention, and conventionally known production methods such as heat sealing using a heat bar (heat jaw), adhesion using hot melt, and center sealing using a solvent are employed. can do.
A package having the sealant of the present invention can be suitably used as a packaging material for various articles such as foods, medicines and industrial products.

Next, the present invention will be specifically described using examples and comparative examples, but the present invention is not limited to the aspects of such examples, and can be changed as appropriate without departing from the spirit of the present invention. Is possible.

<Preparation of polyester raw material>
[Synthesis Example 1]
In a stainless steel autoclave equipped with a stirrer, thermometer and partial reflux condenser, 100 mol % dimethyl terephthalate (DMT) as the dicarboxylic acid component and 100 mol % ethylene glycol (EG) as the polyhydric alcohol component, Ethylene glycol was charged so that the molar ratio was 2.2 times that of dimethyl terephthalate, zinc acetate was used as a transesterification catalyst at 0.05 mol % (relative to the acid component), and the resulting methanol was distilled out of the system. The transesterification reaction was carried out while Then, 0.225 mol % (relative to the acid component) of antimony trioxide is added as a polycondensation catalyst, and the polycondensation reaction is carried out under reduced pressure conditions of 26.7 Pa at 280° C., resulting in an intrinsic viscosity of 0.75 dl/g. A polyester (A) was obtained. This polyester (A) is polyethylene terephthalate. Table 1 shows the composition of polyester (A).

[Synthesis Example 2]
Polyesters (B) to (G) with different monomers were obtained in the same manner as in Synthesis Example 1. Table 1 shows the composition of each polyester. In Table 1, TPA is terephthalic acid, IPA is isophthalic acid, BD is 1,4-butanediol, NPG is neopentyl glycol, CHDM is 1,4-cyclohexanedimethanol, and DEG is diethylene glycol. In the production of polyester (G), SiO2 (Sylysia 266 manufactured by Fuji Silysia Co., Ltd.) was added as a lubricant at a rate of 7,000 ppm relative to the polyester. Each polyester was appropriately chipped. Table 1 shows the compositions of the polyesters (B) to (G).

[Example 1]
Polyester A, polyester B, polyester E, and polyester G were mixed at a mass ratio of 7:60:25:8 as raw materials for the seal layer (A layer), and polyester A, polyester B, and polyester were mixed as raw materials for the heat-resistant layer (B layer). E and Polyester G were mixed in a weight ratio of 48:38:6:8.
The mixed raw materials for the A layer and the B layer were put into separate screw extruders and melted at 270°C. Each molten resin was joined by a feed block in the middle of the flow path, discharged from a T-die, and cooled on a chill roll set to a surface temperature of 30° C. to obtain an unstretched laminated film. The flow path of the molten resin is set so that one side of the laminated film is the A layer and the other side is the B layer (two types of two layers of A layer / B layer), and the thickness ratio of the A layer and the B layer is 50/ The discharge amount was adjusted to 50.
The unstretched laminated film obtained by cooling and solidifying is guided to a longitudinal stretching machine in which a plurality of roll groups are continuously arranged, preheated on preheating rolls until the film temperature reaches 78 ° C., and then stretched 4.1 times. bottom. The film immediately after being longitudinally stretched was passed through a heating furnace set at 100° C. with a hot air heater, and subjected to a 20% relaxation treatment in the longitudinal direction using the speed difference between rolls at the entrance and exit of the heating furnace. After that, the longitudinally stretched film was forcibly cooled by cooling rolls whose surface temperature was set to 25°C.

The relaxed-treated film was guided to a transverse stretching machine (tenter), preheated for 5 seconds until the surface temperature reached 105° C., and then stretched 4.0 times in the width direction (horizontal direction). After the transverse stretching, the film was guided as it was to the intermediate zone and passed through for 1.0 second. In the intermediate zone of the tenter, hot air from the final heat treatment zone and the transverse stretching zone were applied so that when a strip of paper was suspended without the film passing through it, the strip of paper would hang almost completely in the vertical direction. blocked hot air from
After that, the film that passed through the intermediate zone was led to the final heat treatment zone and heat treated at 190° C. for 5 seconds. At this time, 3% relaxation treatment was performed in the width direction by narrowing the clip interval in the width direction of the film at the same time as performing the heat treatment. After passing through the final heat treatment zone, the film was cooled with cooling air at 30°C for 5 seconds. At this time, the film actual temperature at the exit of the tenter was 40°C. A biaxially oriented film with a thickness of 30 μm was continuously produced over a predetermined length by cutting off both edges and winding up into a roll with a width of 600 mm. The properties of the resulting films were evaluated by the methods described above. Table 2 shows the manufacturing conditions.

[Examples 2 to 7]
In Examples 2 to 7, in the same manner as in Example 1, polyester films were continuously formed by variously changing the mixing ratio of raw materials, the first stretching, the intermediate heat treatment, the second stretching, and the final heat treatment conditions. Table 2 shows the manufacturing conditions for each film. In addition, Examples 4 and 5 are sequentially biaxially stretched films in which the first stretching is in the horizontal direction and the second stretching is in the longitudinal direction, and Examples 6 and 7 are simultaneous biaxially stretched films in which the film is stretched simultaneously in the vertical direction and the horizontal direction. (For Examples 6 and 7 in Table 2, the stretching conditions are described in the columns of the first stretching and the second stretching for convenience, but these are stretched simultaneously under the same conditions).

[Comparative Example 1]
Polyester A, polyester B, polyester E, and polyester G were mixed at a mass ratio of 7:75:10:8 as raw materials for the sealing layer (A layer), and polyester A, polyester B, and polyester were mixed as raw materials for the heat-resistant layer (B layer). E and Polyester G were mixed in a weight ratio of 52:30:10:8.
The mixed raw materials for the A layer and the B layer were put into separate screw extruders and melted at 270°C. Each molten resin was joined by a feed block in the middle of the flow path, discharged from a T-die, and cooled on a chill roll set to a surface temperature of 30° C. to obtain an unstretched laminated film. In the laminated film, the molten resin flow path is set so that both sides of the outermost layer are the A layer and the intermediate layer is the B layer (two types of three layers, A layer / B layer / A layer). The discharge amount was adjusted so that the total layer thickness ratio was 50/50.
From the unstretched laminate film obtained by cooling and solidifying, a polyester film was continuously formed in the same manner as in Example 1 by changing the first stretching, intermediate heat treatment, second stretching, and final heat treatment conditions. The properties of the resulting films were evaluated by the methods described above. Table 2 shows the manufacturing conditions.

[Comparative Example 2]
In Comparative Example 2, in the same manner as in Example 1, a polyester film was continuously formed by changing the mixing ratio of the raw materials, the first stretching, the intermediate heat treatment, the second stretching, and the final heat treatment conditions. Table 2 shows the manufacturing conditions for each film.

[Comparative Example 3]
In Comparative Example 3, LIX film (linear low density polyethylene film, registered trademark) L4103-30 μm manufactured by Toyobo Co., Ltd. was used. It is shown in Table 2 together with Examples 1-7 and Comparative Examples 1-2.

<Evaluation method for sealant>
The sealant evaluation method is as follows. If the longitudinal direction and the width direction cannot be determined immediately because the area of the sealant is small, the longitudinal direction and the width direction can be tentatively determined and measured. On the other hand, even if they are different by 90 degrees, there is no particular problem.

[Heat seal strength]
The heat seal strength was measured according to JIS Z1707. Show specific steps. A heat sealer was used to bond the heat-sealed surfaces of the samples together. The heat sealing conditions were an upper bar temperature of 140° C., a lower bar temperature of 30° C., a pressure of 0.2 MPa, and a time of 2 seconds. The adhesive sample was cut so that the seal width was 15 mm. The peel strength was measured using a universal tensile tester "DSS-100" (manufactured by Shimadzu Corporation) at a tensile speed of 200 mm/min. The peel strength is expressed as strength per 15 mm (N/15 mm).

[Deformation rate when tension is applied]
A sample having a size of 30 mm in the longitudinal direction and 4 mm in the width direction was cut out and measured using a thermomechanical analyzer (TMA, manufactured by Seiko Instruments Inc.). The chuck-to-chuck distance was set to 20 mm, and the sample was attached to the probe using a dedicated chuck. After setting the sample, the tension was kept constant at 1.7 N/mm ² (approximately 200 mN in terms of width 4 mm x thickness 30 μm), and the furnace temperature was raised from 30° C. to 160° C. at a rate of 10° C./min. minutes and cooled from 160°C to 30°C at 10°C/min. The deformation rate obtained by this measurement was recorded during heating from 30°C to 140°C and during cooling from 160°C to 30°C. The heat deformation rate from 30° C. to 140° C. and the cooling deformation rate from 160° C. to 30° C. were calculated according to the following formulas 1 and 2, respectively. Regarding the deformation rate, a positive value indicates elongation of the film, and a negative value indicates shrinkage of the film.

Heat deformation ratio = [{length before heating (30 ° C.) - length after heating (140 ° C.)} / length before heating (30 ° C.)] × 100 (%) Equation 1
Cooling deformation rate = [{length before cooling (160 ° C.) - length after cooling (30 ° C.)} / length before cooling (160 ° C.)] × 100 (%) Equation 2

[Warm water heat shrinkage]
Cut the sample into a square of 10 cm × 10 cm, immerse it in warm water at 98 ± 0.5 ° C. for 3 minutes without load and shrink it, then immerse it in water at 25 ° C. ± 0.5 ° C. for 10 seconds, out of the water. After that, the vertical and horizontal dimensions of the sample were measured, and the heat shrinkage rate in each direction was obtained according to the following formula 3. In addition, the measurement was performed twice and the average value was obtained.

Thermal shrinkage = {(length before shrinkage - length after shrinkage) / length before shrinkage} x 100 (%) Formula 3

The thermal shrinkage rate in the vertical and horizontal directions was evaluated according to the following criteria. Judgment criteria are as follows.

Judgment ○ Heat shrinkage rate 5% or less Judgment × Heat shrinkage rate 5% or more

[Adsorption]
The film was cut into a square of 10 cm x 10 cm, two sheets were stacked with the heat-sealed surface facing inward, and the position 1 cm from the end of the film was heat-sealed to prepare a bag. An aluminum cup containing 0.5 ml of the contents was placed in the bag, and the position 1 cm from the film edge was heat-sealed to close and seal the bag. D-limonene (manufactured by Tokyo Chemical Industry Co., Ltd.) and L-menthol (manufactured by Nacalai Tesque Co., Ltd.) were used as the contents. After holding for 20 hours in a 30°C environment, a 5 cm x 5 cm square was cut from the surface of the film bag in contact with the mouth of the aluminum cup, and the cut film was immersed in 4 ml of extraction solvent and extracted with ultrasonic waves for 30 minutes. bottom. 99.8% ethanol (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was used as an extraction solvent. A gas chromatograph "GC-14B" manufactured by Shimadzu Corporation was used to quantify the concentration of the contents in the extraction solution. The gas chromatograph uses "GC-14A Glass ID 2.6φ x 1.1m PET-HT 5% Uniport HP 80/100 (manufactured by GL Sciences)" as the column, FID as the detector, and _N2 as the carrier gas. , a carrier gas flow rate of 35 ml/min, and an injection amount of 1 μl. The amount of adsorption was indicated by the amount of adsorption (μg/cm ² ) per 1 cm ² of the heat-sealed surface, and the low adsorptivity was judged as follows.
Judgment ○ 0 μg/cm ² or more, less than 2 μg/cm ² Judgment △ 2 μg/cm ² or more, less than 10 μg/cm ² Judgment × 10 μg/cm ² or more

<Lamination of Gas Barrier Layer>
A film was unwound from a film roll, and a gas barrier layer was continuously provided on the heat-resistant layer side (when the outermost layer of the film was the same layer on both sides, either layer). Specifically, aluminum was used as a vapor deposition source, and an aluminum oxide (AlOx) thin film was formed by a vacuum vapor deposition method while oxygen gas was introduced in a vacuum vapor deposition machine. Metal rolls were provided at the entrance and the exit of the vapor deposition process, and the film was held by the metal rolls and passed through. The metal rolls were adjustable in speed by a drive motor, and tension was applied to the film by increasing the speed of the downstream rolls (draw) relative to the upstream side. The tension applied to the film was 1.7 N/mm ² (50 N in terms of width 1000 mm×thickness 30 μm). In the sealant of the present invention, since it is necessary for the material for vapor deposition to be adaptable to high tension during vapor deposition processing, the tension is set to be high.

<Evaluation method for gas barrier laminate>
[Gas barrier property]
The water vapor permeability and the oxygen permeability were evaluated as gas barrier properties by the following methods.
Water vapor permeability was measured according to JIS K7126 B method. Using a water vapor permeability measuring device (manufactured by PERMATRAN-W3/33MG MOCON), the direction in which the humidity-conditioned gas permeates from the seal layer side of the laminate to the gas barrier layer side in an atmosphere with a temperature of 40 ° C. and a humidity of 90% RH. The water vapor transmission rate was measured at
Oxygen permeability was measured according to JIS K7126-2 method. Using an oxygen permeation measurement device (OX-TRAN 2/20 manufactured by MOCOM), in an atmosphere of 23°C temperature and 65% RH humidity, in the direction in which oxygen permeates from the seal layer side of the laminate to the gas barrier layer side. Oxygen permeability was measured.
Before measuring the water vapor transmission rate and the oxygen transmission rate, each sample was allowed to stand for 4 hours in an environment with a humidity of 65% RH to adjust the humidity.
The obtained results of water vapor permeability and oxygen permeability were evaluated according to the following criteria.

Judgment ○
Determination of water vapor permeability of 5 [g/(m ² d)] or less and oxygen permeability of 5 [cc/(m ² d atm)] or less ×
Water vapor permeability of 5 [g/(m ² · d)] or more or oxygen permeability of 5 [cc/(m ² · d · atm)] or more

[Heat seal strength]
The 140° C. heat seal strength was evaluated by the same method as the evaluation method for [heat seal strength] described in <Method for evaluating sealant> above.

[Adsorption]
Adsorption of D-limonene and L-menthol was evaluated by the same method as the evaluation method of [adsorption] described in <Evaluation method of sealant>.
Table 3 shows the evaluation results of the obtained gas barrier laminate.

[Film evaluation results]
From Tables 2 and 3, the films of Examples 1 to 7 all satisfied the heat seal strength, the deformation rate when tension was applied, the heat shrinkage rate, and the adsorptivity. was excellent.
On the other hand, the film of Comparative Example 1 exhibited a low gas barrier property even as a gas barrier layered product because of its large deformation rate when tension was applied. Therefore, it was unsuitable as a sealant for vapor deposition.
The film of Comparative Example 2 was unsuitable as a sealant because its heat seal strength was zero.
Since the sealant of Comparative Example 3 had a large deformation rate when tension was applied, the gas barrier property of the gas barrier laminate was low. Furthermore, not only the heat seal strength was low, but also the adsorption of limonene and menthol was inferior, so it was not suitable as a sealant with low adsorption.

INDUSTRIAL APPLICABILITY The polyester-based sealant film of the present invention has little adsorption of the components of the contents, has high heat seal strength in a low temperature range, and has excellent gas barrier properties when provided with a gas barrier layer, and can be suitably used as a sealant film. . Moreover, it is possible to provide a laminate and a package having at least one layer of the polyester sealant film of the present invention.

Claims (5)

A polyester sealant having at least one heat-sealing layer and one heat-resistant layer, each of which is formed of a polyester containing ethylene terephthalate as a main constituent, and which satisfies the following requirements (1) to (3): A laminate in which a gas barrier layer is laminated on a film.
(1) The seal strength when the heat seal layers are sealed at 140 ° C., 0.2 MPa, 2 seconds is 8 N / 15 mm or more and 30 N / 15 mm or less Tension per unit cross-sectional area 1.7 N by thermomechanical analysis (TMA) / mm2, (2) when the temperature is raised from 30 ° C. to 140 ° C. at 10 ° C./min, the deformation rate in the longitudinal direction is 0% or more and 10% or less; While applying a tension per cross-sectional area of 1.7 N/mm2, the temperature was raised from 30°C to 160°C at a rate of 10°C/min, held at 160°C for 1 minute, and then cooled from 160°C to 30°C at a rate of 10°C/min. When the deformation rate in the longitudinal direction is -2% or more and 0% or less (negative value indicates shrinkage) Any of neopentyl glycol, 1,4-cyclohexanedimethanol, 1,4-butanediol, and diethylene glycol as a diol monomer component other than ethylene glycol as a component constituting each polyester constituting the heat-sealing layer and the heat-resistant layer. 2. The laminate according to claim 1, further comprising isophthalic acid as an acid component other than terephthalic acid. A diol monomer component other than ethylene glycol is contained in all the monomer components of each polyester component constituting the heat-sealing layer and the heat-resistant layer, and the content of the diol monomer component satisfies the following (1) to (3). The laminate according to claim 1 or 2, characterized in that:
(1) 30 mol% or more and 50 mol% or less in the heat seal layer (2) 9 mol% or more and 20 mol% or less in the heat-resistant layer (3) The content difference between the heat seal layer and the heat-resistant layer is 20 mol% or more and 35 mol% or less 4. The laminate according to any one of claims 1 to 3, wherein the gas barrier layer is an inorganic thin film layer. A package comprising at least a part of the laminate according to any one of claims 1 to 4.

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