JP2709612B2 - Laminated sheet for tube container body, method for producing the laminated sheet, and tube container - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to pastes for foods and pharmaceuticals, especially containing fragrances and vegetable oils based on terpene-based hydrocarbons, and daily necessities and the like mixed with dyes. TECHNICAL FIELD The present invention relates to a laminated sheet used for a container body of a tube container suitable for filling in a shape, a method for producing the laminated sheet, and a tube container provided with a container body made of the laminated sheet.

[Prior Art] A tube container filled with a fluid to semi-fluid filling material typified by a paste-like material includes a tubular container body having a closed lower end, and a tubular container. It is composed of a shoulder continuous with the upper end of the torso, a mouth and neck continuous with the shoulder, and a cap removably engaged with the mouth and neck. In the case of a tube container in which a substance is filled, it is required to have excellent properties for gas barrier properties, for example, a metal container body, a polyolefin resin layer and a metal foil. A tube container or the like having a container body or the like made of a laminated sheet is used.

[Problems to be Solved by the Invention] By the way, in the conventional tube container having a metal tubular container body, although having excellent gas barrier properties due to the properties of the material of the container body, Depending on the type of filling material to be filled in the container, the metal which is the material of the container body is corroded, which may cause pinholes in the container body, or the filling material is pushed out by squeezing. Due to the structure of the tube container, extremely thin metal foil is used, so the mechanical properties of the container body are poor, for example, when filling the filling or handling the tube container by consumers. In addition, there is a drawback that the tubular container body is easily broken.

Further, in a tube container having a container body made of a laminated sheet of a polyolefin-based resin layer and a metal foil, the polyolefin-based resin layer, which is an inner peripheral surface layer of the container body, contains a volatile oil or a fragrance. Easily attacked by fillings,
The quality of the filling is degraded, and the polyolefin-based resin layer absorbs a flavoring component and an active ingredient having the filling, thereby causing a problem in quality retention characteristics. It also has

On the other hand, the first aspect of the present invention particularly includes pastes such as foods and medicines containing fragrances and vegetable oils based on terpene hydrocarbons, and daily necessities mixed with dyes. In this case, a laminated sheet as a molding material for a container body used for obtaining a tube container that does not degrade the quality characteristics of the filling material is also used. The method for producing a laminated sheet of the first invention, and the third invention is a tube container obtained by using the laminated sheet, particularly containing a fragrance or a vegetable oil of a terpene-based hydrocarbon. Food, pharmaceuticals,
Another object of the present invention is to provide a tube container which can be stored without deteriorating the quality of a paste-like material such as daily necessities in which a dye is mixed.

[Means for Solving the Problems] The laminated sheet for a tube container body according to the first aspect of the present invention includes a surface layer comprising a sealant layer composed of a low-crystalline saturated polyester resin layer and a biaxially oriented saturated polyester resin film layer; An intermediate layer composed of a gas barrier layer, and a back sheet composed of a non-oriented layer made of a low-crystalline saturated polyester resin having a glass transition temperature of 40 ° C. or higher, which is a laminated sheet, and the surface layer in the laminated sheet. It is laminated so that the inner sealant layer becomes the outermost layer,
The back layer in the laminated sheet, i.e., the glass transition temperature is 40 ° C. or more so that the back layer consisting of a non-oriented layer of a low-crystalline saturated polyester resin is the container inner peripheral layer, the tubular container body portion It is molded into.

The method for producing a laminated sheet for a tube container body according to the second invention is particularly directed to a film layer constituting a surface layer in the laminated sheet, that is, a sealant layer comprising a low-crystalline saturated polyester resin layer and a biaxially oriented saturated polyester. A method of forming a surface layer by a resin film layer, wherein a step of obtaining a co-extruded laminated sheet of a low-crystalline saturated polyester resin and a crystalline saturated polyester resin, and A step of stretching at a temperature at which the polyester resin is oriented, using a method of obtaining a surface layer having a laminated structure of a sealant layer composed of a low-crystalline saturated polyester resin layer and a biaxially oriented saturated polyester resin film layer. is there.

Further, the tube container according to the third aspect of the present invention includes the tube container according to the first aspect.
A tube container using the laminated sheet for a tube container body according to the invention, wherein a tube-shaped container body whose lower end is closed, and a shoulder that is continuous with the upper end of the tube-shaped container body And a head consisting of a mouth and a neck continuous with the shoulder, and a cap detachably engaged with the mouth and neck, wherein the shoulder and the shoulder are connected continuously. The head consisting of the mouth and neck is formed of a molded article of a saturated polyester resin having a glass transition temperature of 40 ° C. or higher, and the container body is provided with a sealant layer composed of a low-crystalline saturated polyester resin layer. A surface layer composed of a biaxially oriented saturated polyester resin film layer, an intermediate layer composed of a gas barrier layer, and a back layer composed of an unoriented layer composed of a low-crystalline saturated polyester resin having a glass transition temperature of 40 ° C. or higher, A container body laminated sheet in which the sealant layer in the surface layer is laminated so as to be the outermost layer is formed such that the back surface layer in the laminated sheet is a container inner peripheral layer. is there.

In the laminated sheet for a tube container trunk part of the first invention having the above structure, the surface layer having a laminated structure of a sealant layer formed of a low-crystalline saturated polyester resin layer and a biaxially oriented saturated polyester resin film layer is usually used. , 1
It consists of a sealant layer of about 30μ and a biaxially-oriented saturated polyester resin film layer of about 9-50μ, and the biaxially-oriented saturated polyester resin film layer is back-printed with a printing layer for providing a design effect. Is given by

The biaxially oriented saturated polyester resin film layer in the surface layer is most preferably a film layer made of polyethylene terephthalate resin.

The intermediate layer needs to include a gas barrier layer that provides gas barrier properties, for example,
Al foil having a thickness of about 7 to 40 μm, a biaxially stretched polyamide film having a vinylidene chloride coat layer, a biaxially stretched polyester film having a vinylidene chloride coat layer, a polyester film having an aluminum vapor deposition layer, and ethylene-vinyl alcohol A copolymer resin film or the like is used as a gas barrier layer.

The intermediate layer may be a single layer of the gas barrier layer described above or a composite layer.In the case of a composite layer, the intermediate layer is a composite layer of sheets having gas barrier performance. Of course, it is also good.

Further, the back surface layer is formed of a low-crystalline saturated polyester resin layer having a glass transition temperature of 40 ° C. or higher, and exhibits an excellent effect on perfume resistance in an atmosphere having a glass transition temperature or lower. Things.

When the thickness of the back layer is 5 μm or less, the stability of the resin layer is deteriorated, and the sealing property of the obtained heat-sealed portion may be reduced. When the thickness exceeds 200 μm, the laminated sheet becomes hard and The back layer is preferably formed to have a thickness of about 20 to 100 μm, since a container body having a good container body cannot be obtained.

The sealant layer and the back surface layer are formed of a saturated polyester resin or an amorphous polyester resin having low crystallinity, specifically, a low crystallinity having a crystallinity of 20% or less. It has excellent properties.

The low-crystalline saturated polyester resin in the laminated sheet, that is, the sealant layer and the back surface layer in the laminated sheet are, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol and the like. Formed by a co-condensation polymer of an alcohol component of the above and an aliphatic dicarboxylic acid such as adipic acid and sebacic acid and an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid and diphenyldicarboxylic acid. Specifically, a co-condensation polymer of ethylene glycol with isophthalic acid and terephthalic acid, and a co-condensation polymer of 1,4-cyclohexanedimethanol with ethylene glycol and terephthalic acid, propylene glycol with isophthalic acid and terephthalic acid Etc. are preferred. It is.

In the low-crystalline saturated polyester resin, in the case of a co-condensation polymer in which the aliphatic dicarboxylic acid component in the acid component is 10% by weight or more, the perfume resistance of the saturated polyester resin layer tends to decrease. Because it has
In the back layer, as in the case of a synthetic resin head comprising a mouth and neck and a shoulder in a tube container described later, a cocondensation polymer in which an aliphatic dicarboxylic acid component in an acid component is 10% by weight or less. Is preferred.

Further, in the tube container body laminated sheet according to the first aspect of the present invention, the sealant layer and the back surface layer of the laminated sheet may be provided at the body sticking portion or the lower end closing portion of the container body in the container body. It is preferable that the sealant layer and the back surface layer are formed of the same saturated polyester resin so that a strong joint can be formed at the formed heat-welded portion.

In the laminated sheet for a tube container body according to the first aspect of the present invention, each of the front surface layer, the intermediate layer, and the back surface layer uses, for example, an adhesive such as an adhesive polyolefin resin or a urethane adhesive. It is usually obtained by bonding.

In the method for producing a laminated sheet for a tube container body according to the second invention, the laminated raw sheet obtained by the co-extrusion molding method, that is, the low-crystalline saturated polyester resin layer and the crystalline saturated polyester resin layer Extruded laminated raw sheet, the temperature at which the crystalline saturated polyester resin in the raw sheet is oriented by stretching, that is,
A method for obtaining a surface layer having a laminated structure of a sealant layer composed of a low-crystalline saturated polyester resin layer and a biaxially oriented saturated polyester resin film layer by subjecting to a stretching treatment at a temperature between a glass transition temperature and a melting point. The method uses a method for forming a sealant layer composed of a low-crystalline saturated polyester resin layer that does not orient even when subjected to a stretching treatment.

Incidentally, the crystalline saturated polyester resin layer in the laminated raw sheet comprising the low crystalline saturated polyester resin layer and the crystalline saturated polyester resin layer is formed of a saturated polyester resin having a property of being oriented by a stretching treatment at the stretching temperature. And a saturated polyester resin having a crystallinity of 10% or more is used.

The stretching in the biaxial direction may be a simultaneous biaxial stretching process or a sequential biaxial stretching process, and it is preferable that the film is stretched vertically and horizontally by about 2 to 20 times each.

The tube container of the third invention comprises a tubular container body obtained by using the laminated sheet according to the first invention, and a molded article of a saturated polyester resin having a glass transition temperature of 40 ° C. or higher. It consists of a head of the mouth and neck and a shoulder, and a separately manufactured cap that is detachably engaged with the mouth and neck, and has excellent properties in fragrance resistance.

The shoulder and the mouth and neck in the tube container of the third invention obtained by using the laminated sheet for a tube container body of the first invention have a glass transition temperature of 40 ° C. or more. It may be an integral molded body made of a saturated polyester resin, or may be a combined joined body of individual molded bodies of the shoulder and the mouth and neck made of the resin. Is 40
It is preferable to use an integral molded body of a saturated polyester resin having a temperature of not less than ° C.

Further, the container body in the tube container of the third invention is obtained by blanking a blank sheet by stamping and forming the laminated sheet for the tube container body of the first invention. A body sticking portion is formed by overlapping right side portions and bonding the side portions by heating and pressing.

Note that the mouth and neck portion and the shoulder portion are connected so that a strong joint structure is obtained at the heat-welded portion of the tubular container body portion or at a thermal bonding portion between the tubular container body portion and the shoulder portion. The low-crystalline saturated glass transition temperature of 40 ° C. or higher is applied to the head consisting of the upper part, the sealant layer of the laminated sheet formed on the container body, and the back layer of the laminated sheet also formed on the container body. It is preferable to be formed of the same resin of polyester resin.

[Example] Hereinafter, a specific configuration of the tube container of the present invention will be described with reference to examples.

Example 1 In FIGS. 1 and 2, a 75 μm thick polyester resin having a low crystallinity and a degree of crystallinity of 3%, a cocondensation polymer of ethylene glycol with isophthalic acid and terephthalic acid was used.
And a 300 μm thick second resin layer made of crystalline polyethylene terephthalate resin, obtained by co-extrusion, and then the raw sheet is stretched at a stretching temperature of 200 μm. The film is subjected to simultaneous biaxial stretching at 5 ° C. and stretched 5 times vertically and 5 times horizontally to obtain a thickness of 3
After obtaining a laminate composed of a sealant layer 2 composed of a low-crystalline saturated polyester resin layer having a thickness of μ and a biaxially oriented polyethylene terephthalate resin film layer 3 having a thickness of 12 μ, a triaxially oriented polyethylene terephthalate resin film in the laminate is obtained. By applying a back printing layer m, m by a gravure printing method to the layer 3 surface, a laminated sheet 4 used as a surface layer in the laminated sheet for a tube container trunk portion of the present invention was obtained.

Next, the laminated sheet 4, an intermediate layer 5 made of Al foil having a thickness of 20 μm (manufactured by Nippon Foil Co., Ltd.), and a non-stretched film made of an amorphous polyester resin having a thickness of 60 μm, having a glass transition temperature of 81 ° C. Eastman Kodak Company: PET G 6763 "Layer 6
Are indicated by reference numeral 1 by laminating and bonding, respectively, using adhesive layers S1 and S2 of urethane-based two-part curable adhesive "Takeda Pharmaceutical Co., Ltd .: Takerac A310-Takenate A3". A laminated sheet for a tube container body, which is a product of one example of the first invention to be obtained, is obtained.

Next, using a blank plate obtained by stamping the laminated sheet 1, a tubular shape having a diameter of 35 mm and a height of 15 mm in which the non-stretched saturated polyester resin layer 6 as the back surface layer of the laminated sheet 1 is used as an inner peripheral surface layer. A cylindrical body 7 serving as a container body was formed by overlapping the left and right side portions of the blank plate with each other, and thermally bonding the sealant layer 2 and the back surface layer 6 of the laminated sheet 1 to each other.

On the other hand, a head 10 composed of an integrally formed body of a thin necked neck 8 and a frustoconical shoulder 9 continuous with the lower end of the neck 8.
Was obtained by injection molding using an amorphous polyester resin “glass transition temperature: 81 ° C., manufactured by Eastman Kodak Company: PET G 6763”.

Thereafter, a frustoconical shoulder 9 at the head 10
The lower end of the cylindrical body 7 and the upper end of the above-mentioned cylindrical body 7 are hot-melt-bonded, and the mouth and neck 8 is sealed with a sealing material. Then, a sealing portion 11 formed by hot-melt bonding is formed at the lower end of the cylindrical body 7 to obtain a tube container denoted by reference numeral 12 as an embodiment of the third invention. Was.

Comparative Example 1 Low-density polyethylene film layer having a thickness of 25μ [Mirason
16sp: Surface layer composed of "Mitsui Petrochemical Co., Ltd."
μ biaxially stretched polyester resin film “Ester Film E 5100: Toyobo Co., Ltd.” and a 20 μ thick Al foil were bonded to a urethane-based two-part curable adhesive “Takeda Pharmaceutical Co., Ltd .: Takerac A310-Takenate” A3 "an intermediate layer consisting of a laminated sheet laminated with an adhesive, and a low-density polyethylene film layer with a thickness of 60μ" Milason 16s "as a back layer
p: Mitsui Petrochemical Co., Ltd. ", the surface layer, the intermediate layer, and the back surface layer were contacted with the biaxially stretched polyester film layer in the surface layer and the intermediate layer, respectively, and a urethane-based For comparison consisting of a laminated sheet laminated with an adhesive made of two-part curable adhesive "Takeda Pharmaceutical Co., Ltd .: Takelac A310-Takenate A3" and an injection molded product made of low-density polyethylene resin "Mirason 16sp". A synthetic resin head was used to obtain a comparative tube container filled with 200 g of an orange fruit sauce according to the method of Example 1 below.

[Experiment] Each of the tube containers obtained in Example 1 and Comparative Example 1 was stored at room temperature of 20 ° C. for one month, and then subjected to a sensory test for the taste and aroma of the orange fruit sauce in the filling. In the filling in the tube container of Example 1, orange scent and taste were maintained, but in the filling in the tube container of Comparative Example 1, almost no orange scent remained. Was.

Further, after the tube containers were broken and washed, the odor of the inner peripheral surface layer of each tube container was examined. As a result, the tube container of Example 1 was almost odorless, but the tube container of Comparative Example 1 had no smell. It was confirmed that orange aroma remained, and that the aroma of the orange fruit source had been adsorbed to the inner peripheral surface layer of the tube container.

[Functions and Effects of the Invention] The first invention is directed to a surface layer composed of a sealant layer composed of a low-crystalline saturated polyester resin layer and a biaxially oriented saturated polyester resin film layer, and an intermediate layer composed of a gas barrier layer. Glass transition temperature is 40 ° C. or more and a back layer composed of a non-oriented layer of a low-crystalline saturated polyester resin,
A tube container body laminated sheet that is laminated so that the sealant layer in the surface layer is the outermost layer, and the back surface layer in the laminated sheet is a container body inner peripheral layer, so that a tubular shape is formed. It is molded into the container body.

However, in the tubular container body obtained by using the laminated sheet of the first invention, the inner peripheral surface layer of the container body is formed of a saturated polyester resin layer having a glass transition temperature of 40 ° C. or more. Therefore, in a temperature atmosphere equal to or lower than the glass transition temperature of the saturated polyester resin forming the resin layer, the saturated polyester resin exhibits excellent perfume resistance properties, vegetable oil maintenance properties, and the like.
Lemon essence, toothpaste, shoes, hair dyes, etc., especially foods and pharmaceuticals containing fragrances and vegetable oils from terpene hydrocarbons, and pastes from daily necessities mixed with dyes. Even in the case of being filled, it does not degrade the quality characteristics of the filling and has an extremely excellent effect on the storage performance.

Further, the tubular container body obtained by using the laminated sheet, the heat-welded portion between the surface layer and the back layer in the laminated sheet, a low-crystalline saturated polyester resin as a sealant layer, Since it is formed as a heat-welded portion between the back layer and the low-crystalline saturated polyester resin layer having a glass transition temperature of 40 ° C. or more, it can be used as a body sticking portion in a tube-shaped container body or a closed portion at the container bottom. For example, the bonding portion can be stably formed under mild heat and pressure bonding conditions such as 120 to 160 ° C.

In addition, the surface layer and the back surface layer of the tube-shaped container body have properties excellent in hot-press bonding properties, so that the body-attached portion of the tube-shaped container body has
As shown in FIG. 3, a low-crystalline saturated polyester resin forming the back layer of the laminated sheet located on the outer peripheral surface side of the trunk portion and the front and back layers of the laminated sheet located on the inner peripheral surface side of the trunk portion are formed. Since a state in which the saturated polyester resin flows with the low-crystalline saturated polyester resin and covers the end surface of the laminated sheet located on the inner peripheral surface side of the trunk portion with the saturated polyester resin is formed, the intermediate portion incorporated in the laminated sheet is formed. The end faces of the layers and the adhesive layer between the layers are not exposed to the inside of the container, and the gas barrier layer in the intermediate layer is corroded by the filling in the tube container, or Thus, a good heat-bonded portion can be obtained without fear that the bonding strength of the heat-bonded portion in the portion is reduced.

Furthermore, since the surface layer of the laminated sheet is formed of a biaxially oriented saturated polyester resin film on which a sealant layer made of a low crystalline saturated polyester resin layer is laminated, the biaxially oriented saturated polyester resin film on the surface layer is formed. By applying back printing to the polyester resin film layer surface, it is possible to form a printed layer having excellent robustness and gloss, so that a tubular container body having high design characteristics can be obtained. In addition, the biaxially oriented saturated polyester resin film layer has an action and an effect that the mechanical strength caused by the orientation in the biaxially oriented saturated polyester resin film layer can be utilized.

Further, the second invention provides a laminated sheet obtained by biaxially stretching the co-extruded laminated sheet after obtaining a co-extruded laminated sheet of a low-crystalline saturated polyester resin and a crystalline saturated polyester resin. Is used as a surface layer of a biaxially oriented saturated polyester resin film layer and a sealant layer composed of a low crystalline saturated polyester resin layer, the method for producing a laminated sheet for a tube container body according to the first aspect of the present invention, Utilizing a property of a low-crystalline saturated polyester resin that does not undergo orientation and crystallization even after being subjected to a treatment, and a method of efficiently and reliably obtaining a biaxially oriented saturated polyester resin film having a sealant layer. Is what you do.

Further, in the third invention, a tubular container body having a closed lower end portion, a shoulder portion connected to an upper end portion of the tubular container body portion, and a continuous portion connected to the shoulder portion. In a tube container comprising a mouth and a neck, and a cap removably engaged with the mouth and the neck, the shoulder and the mouth and the neck continuous with the shoulder have a glass transition temperature of 40 ° C. or higher. The container body is formed of a low-crystalline saturated polyester resin layer, a sealant layer and a biaxially oriented saturated polyester resin film layer, and an intermediate layer including a gas barrier layer. Layer and a back layer composed of a non-oriented layer made of a low-crystalline saturated polyester resin having a glass transition temperature of 40 ° C. or higher, and a container body in which the sealant layer in the surface layer is the outermost layer. for It is a tube container formed by a laminated sheet so that the back layer in the laminated sheet becomes an inner peripheral surface layer of the container.

However, in the tube container according to the third aspect, the synthetic resin head combined with the tubular container body obtained by the laminated sheet according to the first aspect has a glass transition temperature. A molded article made of a saturated polyester resin having a temperature of 40 ° C. or higher, and the inner peripheral surface layer of the tube-shaped container body, and the saturated polyester resin forming the synthetic resin head have a glass transition. It exhibits excellent perfume resistance properties in a temperature atmosphere at or below the temperature, and vegetable oil maintenance resistance properties, etc., and has an extremely excellent storage performance that can be stored without deteriorating the quality characteristics of the filling. It is.

Further, the tube container of the third invention is characterized in that the sealant layer and the surface layer in the surface layer of the tube-shaped container body, and furthermore, the shoulder and the mouth and neck, which are the tube container head, are each made of saturated polyester. Since it is formed of resin, the heat-sealing seal between the tubular container body and the heat-bonded portion between the tubular container body and the head can be stably and mildly applied under the conditions of hot and pressure bonding. It also has the function and effect of being able to form.

[Brief description of the drawings]

FIG. 1 is a front view showing an embodiment of the tube container of the third invention, and FIG. 2 is a model showing an embodiment of the tube container body laminated sheet of the first invention. FIG. 3 is a cross-sectional view, and FIG. 3 is a model cross-sectional view showing a state where the container body is adhered to the container body by the laminated sheet shown in FIG. 1: laminated sheet for tube container body, 2: sealant layer, 3:
Biaxially oriented saturated polyester resin film layer, 4: surface layer,
5: Intermediate layer, 6: Back layer, 7: Cylindrical body (tube-shaped container body), 8: Mouth and neck, 9: Shoulder, 12: Tube container.

Claims (3)

(57) [Claims] 1. A surface layer comprising a sealant layer comprising a low-crystalline saturated polyester resin layer and a biaxially oriented saturated polyester resin film layer, an intermediate layer comprising a gas barrier layer, and a low-temperature glass transition temperature of 40 ° C. or higher. A laminated sheet for a tube container body, characterized in that a back layer composed of a non-oriented layer of a crystalline saturated polyester resin is laminated so that a sealant layer in the surface layer is an outermost layer. 2. A sealant layer comprising a low-crystalline saturated polyester resin layer obtained by biaxially stretching a co-extruded laminated sheet of a low-crystalline saturated polyester resin and a crystalline saturated polyester resin, and a biaxially oriented saturated resin. The method for producing a laminated sheet for a tube container trunk according to claim 1, wherein a surface layer formed of a polyester resin film layer is used. 3. A tubular container body having a closed lower end, a shoulder continuous with the upper end of the tubular container body, and a mouth and neck continuous with the shoulder. In a tube container comprising a cap detachably engaged with the mouth and neck, a molded article made of a saturated polyester resin having a glass transition temperature of 40 ° C. or higher, wherein the shoulder and the mouth and neck continuing to the shoulder are formed. And the container body is
A surface layer composed of a sealant layer composed of a low-crystalline saturated polyester resin layer and a biaxially oriented saturated polyester resin film layer, an intermediate layer composed of a gas barrier layer, and a low-crystalline saturated glass transition temperature of 40 ° C. or higher. A back layer made of a non-oriented layer of a polyester resin is laminated with a container body laminated sheet in which the sealant layer in the surface layer is the outermost layer. A tube container formed so as to be a surface layer.