JPH05193045A - Laminated sheet for forming tube vessel drum section - Google Patents

Abstract

PURPOSE:To improve barrier properties, and prevent the generation of a delamination phenomenon in a tube vessel drum section by laminating a barriering oriented resin film layer and an acid modified olefin resin layer laminated on the barriering oriented resin film layer through an organic solvent type anchor coat agent layer. CONSTITUTION:A rear resin layer 8 in a laminated sheet 1 is formed cylindrically as the inner circumferential surface layer of the drum section of a tube vessel. Intermediate layers are composed of a support base material 2 for printing decorating working and a metallic thin-film layer 4 toward the rear resin layer 8 side from the surface resin layer 5 side at that time. A barriering oriented film layer 6 satisfying at least either of steam permeability of 20.0g/m<2>.24hr or less or oxygen gas permeability of 20.0cc/m<2>.24hr or less is formed. The laminated sheet is composed of laminated constitution with an acid modified olefin resin 7 laminated on the film layer 6 through an organic solvent type anchor coat agent layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated sheet formed in the body of a tube container in which a fluid-semi-fluid filling material represented by a paste-like material is enclosed, and particularly contains a highly permeable substance. Disclosed is a laminated sheet for forming a body of a tube container, which exhibits an excellent effect on the storage characteristics of the inner filler even when the inner filler is enclosed.

[0002]

2. Description of the Related Art A tube container in which a fluid-semi-fluid filling material is enclosed is a tube-shaped container body whose lower end is closed and an upper end of the tube-shaped container body. The head portion is composed of a frustoconical shoulder portion and a mouth-neck portion of a narrow neck continuous with the shoulder portion, and a cap that is detachably engaged with the mouth-neck portion.

The container body of this tube container is
A surface resin layer made of a resin having heat sealability, a backside resin layer made of a resin having heat sealability, and an intermediate layer located between these surface resin layer and backside resin layer. A tubular body formed by a laminated sheet in which a barrier layer made of a metal thin film layer is laminated is used.

[0004]

By the way, in the above-mentioned conventional laminated sheet for forming a tube body of the tube container, the back surface resin layer serving as the inner peripheral surface layer of the container body is formed of an olefin resin, and each laminated Since the members are laminated with a solvent-type adhesive, for example, when an internal filler containing a highly permeable substance such as a fragrance, a mineral oil, or an organic polar solvent is stored in a tube container, The highly permeable substance in the filling material inside the tube container permeates the backside resin layer, and then stays between the backside resin layer and the metal thin film layer in the intermediate layer, where the delamination phenomenon occurs. Since it occurs, the function as a tube container cannot be fulfilled.

That is, when a highly permeable substance is enclosed in a tube container made of the conventional laminated sheet, the highly permeable substance permeates the back surface resin layer made of an olefin resin and then comprises a metal thin film layer in the intermediate layer. As a result of being blocked by the barrier layer, this highly permeable substance stays at the interface between the backside resin layer and the metal thin film layer, and the highly permeable substance stored at this interface causes the metal thin film layer and the thin film layer. The adhesive action of the solvent-type adhesive that adheres the laminated member laminated on the back side of the layer is weakened, and the delamination phenomenon occurs in that portion, and the preservation function of the tube container is lost.

On the other hand, the present invention has a high barrier property due to the metal thin film layer, and even when the filling material in the tube container contains a highly permeable substance, the tube container body is (EN) Provided is a laminated sheet for forming a tube body portion which is supplied at low cost without causing a delamination phenomenon in the portion.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides a structure of the above-mentioned conventional laminated sheet, that is, a surface resin layer having heat sealability, a back surface resin layer having heat sealability, and these surface resin layers. In a laminated sheet having an intermediate layer located between the front surface resin layer and the back surface resin layer, as a middle layer between the front surface resin layer and the back surface resin layer, a printing decorative process is performed from the front surface resin layer side toward the back surface resin layer side. Supporting substrate for
Metal thin film layer and 20.0g / m ² · 24hr (40 ℃,
90% RH) or less water vapor permeability and 20.0 cc / m ²
Barrier stretched resin film layer satisfying at least one of oxygen gas permeability of 24 hr (1 atm, 20 ° C., dry) or less, and organic solvent type anchor coat for the barrier stretched resin film layer The conventional problem is solved by utilizing a laminated constitution with an acid-modified olefin resin layer laminated via an agent layer.

In the laminated sheet for forming the body of the tube container according to the present invention having the above-mentioned structure, the surface resin layer and the back surface resin layer are, for example, linear low density polyethylene resin, low density polyethylene resin, medium density polyethylene resin, high density polyethylene. Resin, polypropylene resin, polypropylene homopolymer resin, ethylene-vinyl alcohol copolymer resin, ethylene-ethyl acrylate copolymer resin, ethylene-acrylic acid copolymer resin, ethylene-methacrylic acid copolymer resin, ionomer, poly Acrylonitrile, saturated polyester resin, polyvinyl alcohol resin, etc. are used and formed to a thickness of about 20 to 100 μm.

[0009] Examples of the supporting base material for printing and cosmetic processing include:
A biaxially stretched film having a thickness of about 10 to 100 μ, made of polyethylene terephthalate, polypropylene, nylon, ethylene-vinyl alcohol copolymer resin, cellophane, paper, synthetic paper, or the like is used.

The metal thin film layer fulfills a barrier function in the tube container, and for example, a foil of soft aluminum, copper, iron, nickel or the like having a thickness of about 7 to 50 μ is used.

The barrier stretched resin film layer is laminated on the metal thin film layer and the back side of the metal thin film layer when the high permeable substance in the tube container permeates the back surface resin layer. Barrier stretched resin film layer that prevents the resin layer from reaching the adhesive layer located between it and 20.0 g / m ² · 24 hr (40 ° C, 90% R
H) or less water vapor permeability and 20.0 cc / m ² · 24h
A stretched resin film satisfying at least one of oxygen gas permeability of r (1 atm, 20 ° C., dry) or less, for example, biaxially stretched polyester film, biaxially stretched nylon film, biaxially stretched polypropylene film. , A biaxially stretched ethylene-vinyl alcohol film, a biaxially stretched high density polyethylene film, etc. having a thickness of about 10 to 30 μ are used. The barrier stretched resin film layer is 20.0 g / m ² · 24.
Water vapor permeability of less than hr (40 ° C, 90% RH) and 2
0.0 cc / m ² · 24 hr (1 atm, 20 ° C, dr
Of course, it is preferable that both y) and the following oxygen gas permeability are satisfied.

On the back surface of the barrier stretched resin film layer, an acid-modified olefin resin layer is extruded and laminated using a solvent type anchor coating agent layer coated on the barrier stretched resin film layer surface. This acid-modified olefin-based resin layer functions as an adhesive layer to the backside resin layer having a heat-sealing property.
Methacrylate copolymer, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / ethyl acrylate copolymer, ethylene / methyl acrylate copolymer, ionomer resin, etc., especially acrylic acid A concentration of 3.5 to 14% by weight is preferable. If the acrylic acid concentration is less than 3.5% by weight, the adhesive properties are not good, and if the acrylic acid concentration exceeds 14% by weight, the fluidity of the resin becomes too high.
There is a difficulty in obtaining a uniform adhesive layer. Further, when the acid-modified olefin-based resin layer is extruded and laminated, the surface of the acid-modified olefin-based resin layer to be formed is sprayed with ozone gas to forcibly oxidize the surface to form a backside resin layer having heat sealability. The adhesive strength between and can be improved.

In the laminated sheet for forming the body of the tube container of the present invention having the above-mentioned laminated constitution, a surface resin layer having a heat-sealing property, a supporting base material for printing and decorative processing, a metal thin film layer, and 20.0 g / m ² · 24hr (40 ℃, 90
% RH) or less and water vapor permeability of 20.0 cc / m ² · 2
Each of the barrier stretched resin film layers satisfying at least one of oxygen gas permeability of 4 hr (1 atm, 20 ° C., dry) or less is a dry laminating method using a solvent type adhesive, or a low density polyethylene. Thickness of resin, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-vinyl alcohol copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-ethyl acrylate copolymer, ionomer, etc.
It is laminated by an extrusion laminating method or the like utilizing an extruded resin layer of about μ.

The tube container body obtained by forming the tubular sheet body forming laminated sheet of the present invention into a tubular body has a surface layer on one side of the body forming laminated sheet on the other side. It is formed by overlapping the side parts so that the back surface layers of the side parts are in contact with each other, and adhering the overlapping parts.

[0015]

The tube container body obtained by the laminated sheet for forming the tube container body of the present invention has a barrier stretchability in the laminated sheet even if the filler in the tube container contains a highly permeable substance. Since the resin film layer has the function of retaining this highly permeable substance, the highly permeable substance does not penetrate the barrier stretched resin film layer. Therefore, the highly permeable substance does not stay in the adhesive layer located between the barrier stretched resin film layer and the metal foil layer, and the peeling of the laminated members at the portion is suppressed.

That is, the tube container body obtained by the laminated sheet for forming the body of the tube container of the present invention is
In particular, even when the inner filler containing the highly permeable substance is encapsulated, the highly permeable substance penetrates the barrier stretched resin film layer in the laminated sheet and penetrates into the back surface interface of the metal foil layer. Since it does not occur, delamination does not occur in the metal foil layer, and the effect of excellent storage performance of the internal filler is exhibited.

Further, the laminated sheet for forming the body of the tube container of the present invention has a constitution in which the barrier stretched resin film layer and the acid-modified olefin resin layer are laminated via an organic solvent type anchor coating agent layer. Therefore, it can be supplied at a lower cost than when using an adhesive layer formed by extruding a molten resin.

[0018]

EXAMPLES The concrete constitution of the laminated sheet for forming the body of the tube container of the present invention will be described with reference to production examples.

Example 1 [Fig. 1] In Fig. 1, a makeup treatment 3 by printing on the back surface of a support base material 2 for a print makeup treatment made of a biaxially stretched polyester film "TOYOBO CO., LTD .: E5200" having a thickness of 12µ.
Then, a soft aluminum foil 4 having a thickness of 20 μm “Nippon Foil Co., Ltd.” 4 was added to the decorative surface 3 of the biaxially stretched polyester film 2 at 5.0 g (dry) / m ² urethane type. Adhesive "Takeda Pharmaceutical Co., Ltd .: A515 / A12"
Then, 5.0 g (dry) / m ² of urethane adhesive “Takeda Yakuhin Kogyo Co., Ltd .: A515 / A12” is applied to the surface of the supporting base material 2 for printing and makeup processing. Then, the coated surface has a thickness of 100 which has been subjected to corona discharge treatment.
μ linear low density polyethylene film “Dainippon Resin
The surface resin layer 5 was formed by adhering the corona discharge treated surface of "SR-3".

Then, on the back surface of the soft aluminum foil 4 described above, a urethane adhesive "Takeda Yakuhin Kogyo Co., Ltd .: A51" was used.
5 / A12 ”is used to laminate a barrier stretched resin film layer 6 composed of a biaxially stretched polyester film 12 μm thick“ Toyobo Co., Ltd .: E5200 ”, and further,
A urethane-based anchor coating agent "AD506X / CAT10" is applied on the back surface of the barrier stretched resin film layer 6 by a roll coating method, and then the acid-modified polyolefin having a thickness of 30 μm is applied to the urethane-based anchor coating agent application surface. While extruding and laminating the extruded resin layer 7 made of resin "N1108C: Mitsui Petrochemical Industry Co., Ltd.", ozone gas having a concentration of 20 g / Nm ³ was blown onto the back surface of the extruded resin layer 7. Then, a backside resin layer 8 composed of a 100 μm thick linear low-density polyethylene film “Dainippon Resin Co., Ltd .: SR-3” was extruded and laminated on the surface on which the ozone gas was blown to form one embodiment of the present invention. A laminated sheet 1 for forming a tube container body was obtained as a product.

Comparative Example 1 Instead of the acid-modified polyolefin resin layer 7 in the laminated constitution of the laminated sheet 1 for forming a body of a tube container in Example 1, a low-density polyethylene resin having a thickness of 30 μm “Mitsui Petrochemical Industry Co., Ltd. ): M-11P ”layer, and other configurations are the same as the corresponding configurations of the laminated sheet 1 for forming a barrel of the tube container of Example 1 and the same configuration as the corresponding laminated body for forming a tube container for comparison. Got the sheet.

Comparative Example 2 Laminated low density polyethylene film layer having a thickness of 100 μm, biaxially stretched polyester film layer having a thickness of 12 μm, aluminum foil having a thickness of 20 μm, linear low density polyethylene film layer having a thickness of 100 μm. For comparison, a laminated body for forming a tube container body was obtained by laminating each laminated member by a dry laminating method using a urethane adhesive.

Comparative Example 3 100 μm thick linear low density polyethylene film layer-12 μm thick biaxially stretched polyester film layer-20 μm thick aluminum foil--12 μm thick biaxially stretched polyester film layer-100 μm thick A laminated sheet for forming a tube container body for comparison, which has a laminated constitution composed of the linear low-density polyethylene film layer, was obtained by dry laminating the respective laminated members using a urethane adhesive.

Molding of the body of the tube container The blanks for forming the body of the tube container were obtained by punching the laminated sheet for forming the body of each tube container obtained in Example 1 and Comparative Examples 1 to 3. After that, the left and right side portions of the blank plate are overlapped with each other and heat-bonded to each other so that the back surface resin layer of each of the blank plates is a container inner peripheral surface layer having a diameter of 35 mm and a height of 150 mm. A tube container body made of was molded.

[Experiment 1] The cylindrical body was attached to a mandrel for forming a tube container, and a frustoconical shoulder portion and a neck-neck portion of a narrow neck continuous with the shoulder portion were attached to one end of the cylindrical body. 65% from the open end of the tail end of the cylinder after injection molding of the
Filling with 50 cc of peppermint oil, and subsequently sealing the tail end by heat welding, a tube container having a schematic shape as indicated by reference numeral 9 in FIG. 2 was obtained.

The obtained tube container was fitted with a cap and stored under an environment of 40 ° C. Each tube container,
When stored for 3 weeks, 1 month, 2 months and 3 months,
The body of the tube container was cut and the state of the laminated sheet forming the body was observed. The results are shown in [Table 1].

[0027]

[Table 1]

[Experiment 2] The cylindrical body was attached to a mandrel for forming a tube container, and a frustoconical shoulder portion and a neck-neck portion of a narrow neck continuous with the shoulder portion were attached to one end of the cylindrical body. After forming the head part by injection molding with a high-density polyethylene resin, fill 50 cc of turpentine oil from the open part of the tail end part of the cylinder, and subsequently seal the tail end part by heat welding. Thus, a tube container having a schematic shape as indicated by reference numeral 9 in [FIG. 2] was obtained.

The obtained tube container was fitted with a cap and stored under an environment of 40 ° C. Each tube container,
When stored for 3 weeks, 1 month, 2 months and 3 months,
The body of the tube container was cut and the state of the laminated sheet forming the body was observed. The results are shown in [Table 2].

[0030]

[Table 2]

[0031]

[Effect] A tube container having a container body formed by the laminated sheet for forming a tube container body of the present invention exhibits extremely excellent barrier performance due to the metal thin film layer, and has high permeability in the tube container. Even when the filling material is filled, the delamination phenomenon does not occur in the body of the tube container, and it has an excellent effect on storage performance.
It has the characteristics of excellent utility value in practical use.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing an example of a laminated sheet for forming a tube container body of the present invention.

FIG. 2 is a front view showing a schematic shape of a tube container obtained by using a laminated sheet for forming a tube container body.

[Explanation of symbols]

 1 Laminated Sheet for Forming Body of Tube Container 2 Supporting Material for Printing Cosmetic Processing 3 Cosmetic Processing by Printing 4 Metal Thin Film Layer 5 Surface Resin Layer 6 Barrier Stretched Resin Film Layer 7 Acid Modified Polyolefin Resin Layer 8 Backside Resin Layer 9 Extrusion Tube container

Claims (1)

[Claims] 1. A laminated sheet comprising a surface resin layer having heat sealability, a backside resin layer also having heat sealability, and an intermediate layer located between the surface resin layer and the backside resin layer, In a tube container body forming laminated sheet formed into a tubular body so that the back surface resin layer in the laminated sheet becomes a body part inner peripheral surface layer of the tube container, the intermediate layer includes a back surface resin layer from a back surface resin layer side. Toward the layer side, a supporting base material for printing and makeup, a metal thin film layer, and 20.0 g / m ² · 24 hr (40 ° C, 90% R
H) or less water vapor permeability and 20.0 cc / m ² · 24h
Barrier stretched resin film layer satisfying at least one of oxygen gas permeability of r (1 atm, 20 ° C., dry) or less, and organic solvent type anchor coating agent for the barrier stretched resin film layer 1. A laminated sheet for forming a body part of a tube container, which has a laminated constitution with an acid-modified olefin resin layer laminated via layers.