JP2619247B2 - Laminated material with excellent fragrance retention properties - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a laminated material used for manufacturing various types of packaging bags and containers.

[Prior Art] Conventional laminated materials used for packaging bags, including container trunks, container bottom materials, container lids, etc. of containers for storing various liquid foods and drinks, tea leaves, spices, etc. The inner surface layer on the side that comes into contact with the filling material in the obtained package is composed of a polyolefin-based resin layer, and by utilizing the heat bonding performance of these polyolefin-based resin layers, it can be used for containers and packaging bags of various shapes. It is a general structure to be molded.

[Problems to be Solved by the Invention] By the way, a container using the conventional laminated material in which the inner surface layer is formed of a polyolefin-based resin layer, for example, as a container body, a container bottom, a container lid, etc. And the packaging bag, when forming the polyolefin-based resin layer at the time of obtaining the laminated material, or at the time of forming a container or a packaging bag with the laminated material, the polyolefin-based resin is subjected to thermal decomposition and volatile components such as aliphatic hydrocarbons. Not only has the adverse effect that this volatile component migrates into the filling contained in the container or the packaging bag and causes a change in the flavor or odor of the filling, as well as the above-mentioned lamination. Since the polyolefin-based resin layer in the material easily adsorbs or permeates the flavor component in the filling, it also has a disadvantage that the flavor of the filling changes and is easily damaged.

In order to improve the above-mentioned disadvantages of the polyolefin-based resin layer in the laminated material, the generation of a volatile substance is small, and the polyethylene terephthalate resin layer having a good scent retention performance is laminated so as to be an inner surface layer. However, a single layer of a polyethylene terephthalate resin layer has low heat sealing strength and impact strength, and has been difficult to be put to practical use.

Japanese Patent Application Laid-Open No. 60-48344 describes that the use of a polyester film on which a polyolefin-based resin layer is laminated as a heat seal layer improves the impact resistance. Due to insufficient adhesive strength between the layer and the polyester film
The fact is that sufficient effects have not been obtained.

Further, the present applicant has previously described a first resin layer made of a linear saturated polyester resin having a glass transition temperature of 40 ° C. or more, and a linear saturated polyester resin having a tensile modulus of 10,000 kg / cm ² or less. Proposed a laminated material in which a laminated resin layer with a second resin layer was laminated as a heat seal layer.
Tensile modulus of elasticity in the heat sealing layer is 10,000 kg /
The linear saturated polyester resin layer of cm ² or less is poor in slipperiness of a film-forming raw material at the time of obtaining the layer, stickiness occurs during film formation, or wrinkles of the obtained film are generated, so that it is orderly. There is a drawback that a heat-sealed layer in a deteriorated state cannot be obtained.

On the other hand, the present invention solves all the disadvantages of each of the laminated materials described above, and has a good scent retention performance of the contents in the container or the packaging bag obtained by the laminated materials. It is possible to prevent the occurrence of unpleasant tastes and off-flavors, and to achieve the same heat-bonding ability as that of the conventional hot-press bonding applied to the laminated material, that is, to reduce the heat-bonding ability of the resin layer in the laminated material. An object of the present invention is to provide a laminated material having a property that can be molded into various containers and packaging bags having sufficient thermal adhesive strength by using molding means.

[Means for Solving the Problems] The laminated material having excellent fragrance retention properties according to the first aspect of the present invention is made of a linear saturated polyester resin having a glass transition temperature of 40 ° C. or higher. A resin layer, a second resin layer made of a linear saturated polyester resin having a tensile modulus of 10,000 kg / cm ² or less, and a third resin layer made of a linear saturated polyester resin having a glass transition temperature of 40 ° C. or more And
It is composed of a three-layer co-extruded laminated resin sheet laminated so that the second resin layer becomes a core layer.

Further, the laminated material having excellent fragrance retention properties according to the second invention has a first resin layer made of a linear saturated polyester resin having a glass transition temperature of 40 ° C. or more, and a tensile elastic modulus. A second resin layer made of a linear saturated polyester resin having a glass transition temperature of 40 ° C. or more and a second resin layer made of a linear saturated polyester resin having a glass transition temperature of not more than 10,000 kg / cm ^2, It is composed of a three-layer co-extruded laminated resin sheet laminated so that the layer becomes a core layer, and an adhesive and laminated sheet with a separately manufactured base material for packaging material.

A resin layer of a linear saturated polyester resin having a glass transition temperature of 40 ° C. or more, which forms both surface layers of the laminated material of the first invention, and a surface of the laminated resin layer of the laminated material of the second invention A resin layer of a linear saturated polyester resin having a glass transition temperature of 40 ° C. or more forming a layer,
That the resin layer composed of the linear saturated polyester resin has excellent fragrance retention at a temperature lower than the glass transition temperature of the linear saturated polyester resin constituting the resin layer, and And the contents inside the packaging bag are usually
In view of the fact that the resin layer is placed in an atmosphere having a temperature of less than 40 ° C., the resin layer made of the linear saturated polyester resin can have excellent fragrance retention performance.

In addition, the resin layer of the linear saturated polyester resin having a glass transition temperature of 40 ° C. or higher has excellent thermal adhesive strength to the thermal adhesive portion in a container or a packaging bag obtained by the laminate of the present invention. It is preferable that a resin having as low a crystallinity as possible is used from the viewpoint that it can be obtained.

A linear saturated polyester resin layer having a glass transition temperature of 40 ° C. or higher is formed of, for example, an alcohol component such as ethylene glycol, propylene glycol, 1,4-butadiol, 1,4-cyclohexanedimethanol and an adipic acid, sebacic acid or the like. Dicarboxylic acid components of aliphatic dicarboxylic acids and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and diphenylcarboxylic acid, specifically, ethylene glycol and terephthalic acid, ethylene glycol and isophthalic acid and terephthalic acid, and 1,4- Co-condensation polymers such as cyclohexane dimethanol and isophthalic acid and terephthalic acid, and propylene glycol and isophthalic acid and terephthalic acid can be used, but the co-condensation polymer in which the aliphatic dicarboxylic acid component in the acid component is 10% by weight or more. In this case, the saturated polyester resin layer of this copolymer is Is unfavorable because it has a tendency for the fragrance retention performance to decrease.

Tensile elastic modulus in the laminated material of the present invention is 10,000 kg / cm ²
The following linear saturated polyester resin may be the same type of linear saturated polyester resin as the above-mentioned linear saturated polyester resin having a glass transition temperature of 40 ° C. or higher, but the linear saturated polyester resin is pulled. In order to lower the elastic modulus, a linear saturated polyester resin having a tensile elastic modulus of 10,000 kg / cm ² or less obtained by using a resin group dicarboxylic acid as an acid component, or using a glycol component having a large number of carbon atoms, etc. used.

In the laminated material of the second invention, the first resin layer made of the linear saturated polyester resin having a glass transition temperature of 40 ° C. or more and a linear saturated polyester resin having a tensile elastic modulus of 10,000 kg / cm ² or less. A second resin layer of a polyester resin,
A third resin layer of a linear saturated polyester resin having a glass transition temperature of 40 ° C. or higher, and a co-extruded laminated sheet laminated such that the second resin layer becomes a core layer. The laminated resin layer is bonded and laminated to a packaging material base material, and is generally bonded by, for example, a polyethylene resin or an isocyanate-based adhesive. The base material for packaging material on which the laminated resin layer composed of the co-extruded laminated sheet is laminated is the second base material.
When the laminated material of the invention of the invention is used as a material for a soft packaging container such as a stand pouch, generally, Al
A laminated sheet of foil, a biaxially oriented polyester film, a biaxially oriented polypropylene film, or the like is used.Also, when a laminated material for a container such as a gobel top paper container or a brick paper container is used, generally, an Al foil is used. A laminated sheet composed of a sheet, a paper layer, a polyolefin resin layer, and the like is used.

[Function and Effect of the Invention] The laminated material having excellent fragrance retention properties of the first invention has a first resin layer of a linear saturated polyester resin having a glass transition temperature of 40 ° C. or more. A second resin layer made of a linear saturated polyester resin having a tensile modulus of 10,000 kg / cm ² or less, and a third resin layer made of a linear saturated polyester resin having a glass transition temperature of 40 ° C. or more. And a co-extruded laminated resin sheet laminated so that the second resin layer becomes a core layer, and a laminate having excellent fragrance retention properties according to the second invention. The material is composed of a first resin layer made of a linear saturated polyester resin having a glass transition temperature of 40 ° C. or more, and a second resin layer made of a linear saturated polyester resin having a tensile modulus of 10,000 kg / cm ² or less. With a glass transition temperature of 40 ° C or higher And a third resin layer made of a linear saturated polyester resin. The co-extruded laminated resin sheet laminated so that the second resin layer becomes a core layer is a separate packaging material. It consists of a laminated sheet adhered to the substrate for use.

However, in the laminated sheet of the present invention, in a packaging bag or a container using the laminated sheet as a packaging material, a linear saturation in which the surface in contact with the filling, that is, the inner surface layer has a glass transition temperature of 40 ° C. or more. Since it is composed of a resin layer of a polyester resin, the fragrance of the filling is not absorbed by the packaging material, and therefore, the change in taste and aroma of the filling is effectively prevented. And excellent perfume retention performance is achieved.

Further, in the laminated sheet of each of the present invention, the packaging bag or container using the laminated sheet as a packaging material has a glass transition temperature of 40 ° C. or higher which constitutes the surface in contact with the filling, that is, the inner surface layer. The second resin layer made of a linear saturated polyester resin having a tensile modulus of 10,000 kg / cm ² or less in contact with the resin layer made of the linear saturated polyester resin. Due to the flexibility, the impact applied to the packaging material is effectively absorbed, and as a result, a packaging bag or a container having a heat-welded portion having excellent properties with respect to impact resistance can be obtained.

Further, in the laminated sheet of each of the present invention, a first resin layer of a linear saturated polyester resin having a glass transition temperature of 40 ° C. or more, and a linear saturated polyester resin having a tensile elastic modulus of 10,000 kg / cm ² or less. A second resin layer according to
A third resin layer made of a linear saturated polyester resin having a glass transition temperature of 40 ° C. or more;
A resin layer of a linear saturated polyester resin having a glass transition temperature of 40 ° C. or higher, wherein a coextruded laminated sheet is used in which the resin layer is laminated as a core layer. With a resin layer made of a linear saturated polyester resin with a tensile modulus of 10,000 kg / cm ² or less, it has good adhesion performance between each other and has the above-mentioned properties that are excellent in fragrance retention performance and impact resistance. The action with the part is synergistically and effectively achieved.

Further, since the laminated sheet composed of the first resin layer, the second resin layer, and the third resin layer used in the laminated sheet of the present invention is a laminated sheet formed by co-extrusion, When obtaining a linear saturated polyester resin having an elastic modulus of 10,000 kg / cm ² or less as a single sheet,
When obtaining a laminated sheet in which the layer is exposed on the surface, for example, the slipperiness of the film forming raw material is poor, and no sticking occurs during film forming, and no wrinkles are generated in the obtained film. Thus, an orderly laminated material can be obtained.

[Example] Hereinafter, a specific configuration of a laminate having excellent fragrance retention properties of the present invention will be described with reference to the illustrated examples.

Example 1 In FIG. 1, one example of a laminated material having a property excellent in fragrance retention performance of the present invention, which is indicated by reference numeral 1, is 170 mm × 1
30mm 4-side seal pouch packaging material, 12μ thick
m of biaxially stretched polyethylene terephthalate film 2 and 9 μm thick Al foil 3
And a laminated resin sheet 6 laminated on the packaging material substrate 4 via an adhesive layer 5 of an isocyanate-based adhesive.

The laminated resin sheet 6 has a glass transition temperature of 81 ° C.
A 10 μm thick first resin layer 7 made of a linear saturated polyester resin [PET G 6763, manufactured by Eastman Kodak Co., Ltd.], and a linear saturated polyester resin having a tensile modulus of 2000 kg / cm ² [Toyobo Co., Ltd. Co., Ltd., Byron GM-900] having a thickness of 60 μm, and a third resin layer 9 having a thickness of 10 μm and made of the same resin as the first resin layer 7. And obtained by a co-extrusion T-die molding method.

Comparative Example 1 A isocyanate-based adhesive was applied to an Al foil surface of a base material for a packaging material comprising a laminated sheet of a biaxially stretched polyethylene terephthalate film layer having a thickness of 12 μ and an Al foil having a thickness of 9 μ. A laminate material [A] for comparison was formed by forming a polyolefin-based resin layer having a thickness of 70 μm using an ethylene-pentene / 1 copolymer [Mitsubishi Petrochemical Co., Ltd .: Ultzex 2021 L]. I got

Comparative Example 2 A glass transition temperature of 81 was applied to an Al foil surface of the base material using an isocyanate-based adhesive on a base material for a packaging material having the same configuration as the base material 4 for the packing material used in Example 1. ° C linear saturated polyester resin [Eastman Kodak Co., Ltd .: PET G
6763] to form a polyester resin layer having a thickness of 70 μ, thereby obtaining a laminated material [B] for comparison.

Comparative Example 3 A laminated resin sheet comprising a 70 μm-thick resin layer made of a linear saturated polyester resin having a tensile modulus of 2000 kg / cm ² and a 10 μm-thick resin layer made of a linear saturated polyester resin having a glass transition temperature of 81 ° C. When formed by a co-extrusion T-die molding method and wound up on a roll, the blocking phenomenon between the front and back surfaces of the wound sheet was severe, and it was impossible to rewind the wound sheet.

[Experiment] Using each of the above-described laminated material of the present invention and the laminated materials [A] and [B] for comparison, 170 mm × 130 mm containing 200 ml of orange juice inside.
Was produced such that the packaging material substrate surface of each laminated material was the outer surface. In addition, the sealed packaging bag is obtained by bonding the inner peripheral layers of the bag by heat sealing,
This is obtained by heat-sealing the four peripheral edges of the laminated material.

The impact resistance of the sealed packaging bag was examined according to the degree of damage that occurred when the sealed packaging bag containing the orange juice was dropped on the floor from a height of 1.2 m. Also, after leaving each sealed bag in a 40 ° C. atmosphere for one week, the bag is opened, and a sensory test of the flavor of the orange juice inside is carried out. The presence or absence of a sex component was investigated, and the fragrance retention performance of each of the sealed packaging bags was compared.

 The results are shown in Table 1.

[Brief description of the drawings]

The figure shows one of the laminated materials having excellent fragrance retention properties of the present invention.
It is sectional drawing which shows an Example article modelly. 1: Laminated material with excellent fragrance retention properties, 4: Base material for packaging material, 6: Co-extruded laminated resin sheet, 7: By linear saturated polyester resin having a glass transition temperature of 40 ° C or higher First resin layer, 8: Second resin layer of linear saturated polyester resin having a tensile modulus of 10,000 kg / cm ² or less, 9: 40 ° C.
A third resin layer made of a linear saturated polyester resin having the above glass transition temperature.

Claims (2)

(57) [Claims] 1. A first resin layer made of a linear saturated polyester resin having a glass transition temperature of 40 ° C. or more, and a second resin made of a linear saturated polyester resin having a tensile elastic modulus of 10,000 kg / cm ² or less. Coextrusion in which a layer and a third resin layer of a linear saturated polyester resin having a glass transition temperature of 40 ° C. or higher are laminated such that the second resin layer becomes a core layer. A laminated material having properties excellent in fragrance retention performance, comprising a laminated resin sheet. 2. A first resin layer of a linear saturated polyester resin having a glass transition temperature of 40 ° C. or more, and a second resin layer of a linear saturated polyester resin having a tensile modulus of 10,000 kg / cm ² or less. Co-extrusion in which a layer and a third resin layer of a linear saturated polyester resin having a glass transition temperature of 40 ° C. or higher are laminated such that the second resin layer becomes a core layer. A laminated material having excellent fragrance retention properties, characterized in that the laminated resin sheet is bonded to a base material for a packaging material and is composed of a laminated sheet.