JPS6241942B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a plastic squeeze container,
More specifically, it has air bag prevention properties (non-recovery properties) that are desirable for squeezing containers, and also has oxygen, moisture,
This invention relates to a plastic squeeze container that has barrier properties against aromas, etc., light shielding properties, and metallic appearance. (Prior Art) Conventionally, squeeze containers, such as extrusion tubes for storing highly viscous liquid products such as toothpaste, cosmetics, or foods, and viscous foods such as ketchup, mayonnaise, jam, and chocolate, have been used. Squeeze bottles made of various flexible laminates are known. Such plastic flexible laminates are generally
It consists of an oxygen barrier layer made of saponified ethylene-vinyl acetate copolymer, nylon, etc. as an intermediate layer, and layers of olefin resin such as polyethylene laminated on both sides (Japanese Patent Application Laid-Open No. 55-5311). . That is, when forming a tube, these flexible laminated sheets are overlapped and bonded to form a cylindrical shape, and one end of this cylindrical body is provided with a threaded extrusion port formed by resin injection molding. A continuous conical shoulder is adhered to the cylindrical body, and the other end of the cylindrical body is closed by fusion or the like. Further, when forming a squeeze bottle, the multilayer parison made of the above-mentioned laminated structure is hollow-molded in a split mold to form a bottle. (Problems to be Solved by the Invention) However, conventionally known plastic squeeze containers have various problems related to the fact that the plastic is used as a constituent material. For example, unlike squeeze containers made of aluminum foil or a laminate of aluminum foil and plastic, squeeze containers made of plastic are not susceptible to air bags, such as applying a certain pressure deformation and then returning to the original container shape when the deformation is released. In other words, the resiliency is excessively high, and for this reason, when the container is sealed with a lid and restored after use, a large amount of air is sucked into the container, resulting in the disadvantage that the contents deteriorate due to the oxygen inside the container. arise. In addition, even if the remaining amount of the container becomes small due to excessive restorability, the contents cannot be squeezed out from the mouth unless the container wall is pressed and deformed to a considerable extent. In addition, due to the fact that air is contained in the container, during the above-mentioned press deformation, a significantly larger amount of the contents than the amount used at one time may be extruded or scattered as is or together with the air. This results in drawbacks such as loss of contents and contamination of clothing, tables, tablecloths, etc. In addition, in plastic squeezing containers, in order to provide easy deformability necessary for squeezing,
The container walls must be fairly thin, which reduces oxygen permeation through the container walls to the contents.
Another problem is that fragrance and moisture permeate from the contents to the outside air at a level that cannot be ignored. Furthermore, these plastic squeeze containers have the property of transmitting light, and deterioration of the contents by light rays poses a serious problem. (Means for solving the problems) In order to solve the above-mentioned problems, the present invention has the following features:
Together with the oxygen barrier resin layer and the moisture-resistant resin layer, a layer of a blend in which flake pigments or flake fillers are distributed in layers in a thermoplastic resin is used as a component of the wall of the squeeze container. . (Function) In the present invention, by providing a layer of a blend in which flake pigments or flake fillers are distributed in layers in a thermoplastic resin, air bag prevention performance is significantly improved. be. That is, when a layered mixture of a thermoplastic resin and a flake pigment, etc. is melt-extruded simultaneously with an oxygen barrier resin layer and a moisture-resistant resin layer, the flake pigment, etc. flows along the extrusion direction and in the direction of the vessel wall surface. Orient along. The orientation of the flake pigments etc. gives the container wall of this multilayer structure a tendency to plastically deform under stress. Thus, as shown in the examples below, the restoring force when a certain pressure deformation is applied to the container body and then released is lower than that of a conventional container (container without a blend layer containing flake pigment, etc.). teeth
While the weight is on the order of 210 to 1000 g, in the squeeze container of the present invention, it is on the order of about 1/2 to 1/4 when compared with the same thickness, resulting in a remarkable improvement in air bag prevention performance. is obvious. Furthermore, since the flake pigment or the flake pigment is distributed in a layered manner in the blend layer, the container of the present invention has light-shielding properties, making it possible to effectively prevent the contents from being altered by light rays. Furthermore, it has a metallic appearance. In addition, by forming a blend layer containing a thermoplastic resin and a flake pigment, etc. into a laminated structure together with an oxygen barrier resin layer and a moisture-resistant resin layer, it is possible to make the flake pigment etc. It has an important meaning in aligning along the . That is, a blend containing flake pigment etc.
Under conditions that allow extrusion molding as a single layer, the orientation of flake pigments, etc. tends to be in a very random direction, making it difficult to maintain the restoring force at a small level during pressure deformation. Under high temperature extrusion conditions where orientation occurs, the melt tension of the blend is too low, making it difficult to form into containers. On the other hand, according to the present invention, when the flake pigment blend layer is extruded together with the oxygen barrier resin layer and the moisture resistant resin layer, both resin layers act as a supporting carrier for the blend layer, and the flake pigment blend layer is extruded. It is possible to form a container by squeezing while imparting a layered orientation. Further, since the oxygen barrier resin layer and the moisture-resistant resin layer are provided separately from the blend layer, it is easy to maintain elasticity, impact strength, etc. within the desired range required for the container. In other words, the blend layer containing flake pigment etc. tends to have slightly lower mechanical properties, but
Due to the presence of each of the above-mentioned layers, the disadvantages caused by such a tendency can be easily prevented. Furthermore, the presence of a resin layer with excellent oxygen barrier properties (oxygen barrier layer) and a resin layer with excellent water vapor barrier properties (moisture-resistant resin layer) provides excellent barrier properties against oxygen, water vapor, fragrance, etc. In the present invention, since the flake pigments are distributed in layers in the blend layer, gas barrier properties are further improved. (Effects of the Invention) According to the present invention, the resiliency after squeezing out the contents is suppressed to a low level compared to conventionally known plastic squeeze-out containers, that is, the plastic has excellent air bag prevention properties. A squeezed container is obtained. Furthermore, the squeeze container of the present invention has improved gas barrier properties and light shielding properties, and can effectively prevent deterioration of the contents. Moreover, it has a metallic appearance, and its commercial value is significantly improved. (Embodiment) In FIGS. 1, 2 and 3 showing a specific example of the tube package of the present invention, the tube package consists of a tube body 1 and a lid 2, and the tube body 1 will be explained in detail later. A threaded extrusion port 3 integrally formed by hollow molding of the multilayer parison described above;
It has a flexible conical shoulder portion 4 and a cylindrical body portion 5 that are connected thereto. In FIG. 3, which shows an enlarged wall section of a multilayer parison constituting each of these parts, the body wall 5 includes an oxygen barrier thermoplastic resin layer 6, a moisture-resistant thermoplastic resin layer 7, and an intervening layer between these two layers. It is composed of a layer 8 of a resin blend containing flake pigment. In FIGS. 1 and 2, this cylindrical body 5 has a cut edge 9 at which the facing inner layers 10, 10 of the body are overlapped and fused. , forming the bottom. Oxygen Barrier Resin Layer In the present invention, the most suitable example of the oxygen barrier resin layer 6 is an ethylene-vinyl alcohol copolymer, especially a vinyl alcohol monomer content of 40 to 85 mol%, particularly 50 to 80 mol%. % can be mentioned. Such ethylene-
Vinyl alcohol copolymers are copolymers of ethylene or a combination of a major part of ethylene and a small amount of other olefins such as propylene and vinyl esters of lower fatty acids such as vinyl formate, vinyl acetate, and vinyl propionate, especially ethylene. - Obtained by saponifying a vinyl acetate copolymer to a degree of saponification of 96% or more, particularly 99% or more. Other examples of oxygen barrier resins include nylon resins, especially nylon 6, nylon 8, nylon
11, nylon 12, nylon 6, 6, nylon 6,
10, nylon 10,6, or nylon 6-6,6
Copolymers and the like can be mentioned. The oxygen barrier resin can be used in the form of a so-called blend. For example, a blend of an ethylene-vinyl alcohol copolymer and a nylon resin can be used, and a blend of an ethylene-vinyl alcohol copolymer and a nylon resin can also be used. /or Blends mainly composed of nylon and containing small amounts of other resins, such as polyethylene, ethylene-vinyl acetate copolymers, or ionomers, may also have oxygen permeability coefficients of 5.5×
10 ^-12 cc・cm/cm ²・sec・cmHg (37℃, 0%RH)
In particular, if it is within the range of 4.5×10 ⁻¹² cc·cm/cm ² ·sec·cmHg or less, it can be used for the purpose of the present invention. Moisture-resistant resin layer The moisture-resistant resin layer 7 has low permeability to water vapor and preferably has an elastic modulus (E ₀ ) of 700.
Resins in the range from 700 to 4000 Kg/cm ² , particularly 700 to 4000 Kg/cm ² , most preferably olefinic resins are used. As the olefin resin, any olefin resin known per se may be used, such as low, medium,
or polyolefins such as high-density polyethylene, isotactic polypropylene, polybutene-1,4-methylpentene-1, and ethylene-propylene copolymers; or ethylene-vinyl acetate copolymers, ethylene-acrylic acid ester copolymers, Examples include olefin copolymers mainly composed of olefins such as ionomers; or blends thereof. In order to improve the squeezing characteristics of the olefin resin layer, a small amount of elastomer such as polyisobutylene, butyl rubber, styrene butadiene rubber, ethylene propylene rubber, etc. The amount can be blended. In the present invention, in terms of the most suitable squeezing characteristics, it is preferable to use an olefinic resin having an elastic modulus in the range of 700 to 4000 kg/ ^cm2 , particularly low-density polyethylene, ethylene-vinyl acetate copolymer, or ionomer. Good. Blend Layer In the present invention, as the thermoplastic resin constituting the blend layer 8, an olefin resin, an acid-modified olefin resin, or a blend thereof is preferably used. That is, a blend layer containing an olefin resin exhibits excellent adhesion to the olefin resin layer as a moisture-resistant resin layer, while a blend layer containing an acid-modified olefin resin or a polymer blend thereof exhibits excellent adhesion to the moisture-resistant resin layer. Since it exhibits adhesion to both the olefin resin layer as the resin and the ethylene-vinyl alcohol copolymer layer as the oxygen barrier resin, it is particularly advantageous for the purpose of the present invention. As the olefin resin, any olefin resin exemplified with respect to the moisture-resistant resin can be used. The acid-modified olefin resin used is one obtained by graft polymerizing the above-mentioned olefin resin with an ethylenically unsaturated carboxylic acid or its anhydride. Suitable examples of acid monomers used for modification are as follows. A Ethylenically unsaturated carboxylic acid: acrylic acid, itacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid,
5-norbornene-2,3-dicarboxylic acid. B Ethylenically unsaturated carboxylic anhydride: maleic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, tetrahydrophthalic anhydride. These acid-modified monomers have a carboxyl group concentration of 1 to 600meq/100g, especially 10 to 600meq/100g.
It is desirable to graft at a concentration of 500meq/100g polymer. It is also possible to use a blend of an acid-modified olefin resin and an olefin resin so that the acid concentration falls within the above range. As the flake pigment or flake filler to be incorporated into the blend layer, mica and metal frame pigments, such as flake pigments of aluminum, copper, lead, etc., are preferably used. The aspect ratio of the flake pigment, etc. used, ie, the ratio of maximum flake diameter/flake thickness, is preferably 20 or more, and the maximum diameter of the flake pigment, etc. is preferably in the range of 100 to 1000μ. These flake pigments are preferably contained in an amount of 5 to 100 parts by weight, particularly 10 to 50 parts by weight, per 100 parts by weight of resin. That is, if the amount is less than the above range, the improvements in the various properties described above will be unsatisfactory, while if it is more than the above range, the mechanical properties of the blend layer itself will deteriorate significantly. Layer Structure The squeeze container of the present invention can have any layer structure as long as it contains the oxygen barrier resin layer (A), the moisture-resistant resin layer (B), and the blend layer (C) as essential components. Of course, if adjacent resin layers do not have adhesive properties, an adhesive layer (D) such as acid-modified olefin resin may be interposed. A suitable example of a multilayer structure is as follows. (i) Three-layer configuration B/C/A, (ii) Four-layer configuration B/C/A/C, B/C/D/A (iii) Five-layer configuration B/C/A/C/B B/ C/D/A/C' (iv) Six-layer configuration B/C/D/A/D/B B/C/D/A/D/C B/C/D/A/C'/B (v ) Seven-layer structure B/C/D/A/D/C/B In the squeeze container of the present invention, for ordinary aqueous contents, olefin-based containers are used for both hygiene and moisture barrier properties. It is desirable to use resin as the innermost layer. Furthermore, for oily contents, it may be desirable to use an ethylene-vinyl alcohol copolymer as the innermost layer. For many purposes, an olefin resin as a moisture-resistant resin is used as the inner and outer surface layers, an ethylene-vinyl alcohol copolymer as an oxygen barrier resin is used as an intermediate layer, and a frame-shaped pigment-containing resin is used as the intermediate layer. Preferably, there is an intervening layer. The thickness of each resin layer is determined so as to simultaneously achieve the required gas barrier properties and air bag prevention properties. That is, the thickness of the oxygen barrier resin layer is t
_A , when the thickness of the moisture-resistant resin layer is t _B and the thickness of the flaky pigment blend layer is t _C , 0.20≧t _A /(t _A +t _B +t _C )≧0.01 0.6≧t _B /(t _A The thickness of each layer is set so that +t _B +t _C )≧0.1 0.9≧t _C /(t _A +t _B +t _C )≧0.4, and the overall thickness is set to 0.17 to 1.0 mm, especially 0.3 to 0.7 mm. It is better. Manufacture of Container The squeeze container of the present invention can be produced by simultaneously melting and extruding each of the resin layers described above into a multilayer parison and blow molding it into a squeeze bottle, or by heat sealing the end edge of the bolt to make a tube container. It can be obtained by Alternatively, each resin layer may be formed into a multilayer film and stacked and fused to form a tube container. In Figures 4-A to 4-F for explaining the method for manufacturing the squeeze container of the present invention, extruders 11 whose number corresponds to the type of resin layer constituting the multilayer parison are shown.
(Only one extruder is shown in the drawing) is used to co-melt extrude the oxygen barrier resin, moisture resistant resin and flake pigmented resin through a multilayer die 12 into a multilayer parison 13 ( Figure 4-A). A pair of split molds 14, 14 are provided along the direction in which the multilayer parison 13 is extruded. The split molds 14, 14 have a cavity 15 defined by a threaded extrusion opening of the tube container, a conical shoulder and an inner wall for the cylindrical body, and a base insert 16 for pinching off the parison 13. We are prepared. In FIG. 4-B showing the blow molding process, the multilayer parison 13 extruded from the die is sandwiched between split molds 14, 14, and its lower end is pinched off with the base insert 16 to form a bottom part, and this parison is A flexible bolt 17 (see Figure 4-C) equipped with a threaded extrusion port, a conical shoulder, a cylindrical body, and a bottom connected thereto is created by blowing fluid such as air, nitrogen, or water vapor into the bolt 13. ) is blow molded. The thus formed flexible bolt 17
In the trimming step shown in FIG. 1-C, the bottom 19 is cut at the end edge of the body connected thereto using a suitable cutter 18 and removed. Next, in FIG. 4-D, the tube body 1 with the lid 2 covering the threaded opening is turned upside down, and the filling nozzle 2 is inserted through the end edge 20 of the tube body 1.
1, a viscous liquid content 22 is filled into the tube body. Furthermore, in FIG. 4-E, the tube body 2 filled with the contents 22 is heated if necessary after the internal atmosphere (air, etc.) is substantially eliminated by means such as pressing.・Seal bar 23
The inner layers facing each other are sandwiched by a heat-sealing mechanism such as the one shown in FIG. In the present invention, melt extrusion of a multilayer parison comprises:
It can be carried out at a temperature above the melting temperature of the resin and below its decomposition temperature, in particular at a temperature of 185° to 230° C., under conditions known per se. In addition, the hollow molding of the multilayer parison should be carried out under conditions known per se, except that the body and conical shoulder of the bolt should have a basis weight that provides flexibility suitable for squeezing, etc. Therefore, flexible bolts can be easily manufactured using, for example, a rotary or intermittent blow molding machine. Furthermore, the stacking and fusing of the inner layers at the opening edge of the container can be performed using any mechanism other than a heat seal bar such as high frequency fusing, ultrasonic fusing, or the like. It should also be understood that the manufacture of the squeeze bottle is carried out by means similar to the blow molding described above, omitting the cutting of the bottom. The squeeze-out container of the present invention thus obtained can be printed on the outer wall of the container, and in this case, in order to prevent the printing from coming off, it is possible to print on the outer wall of the container using commonly used epoxy, acrylic, or epoxy-vinyl containers. It is desirable to apply a top coat. Furthermore, the squeeze container of the present invention may be a so-called tube container, a squeeze bottle, or any other modification.
Various purposes can be used in the form of containers for the purpose of expressing the contents. (Preferred Embodiment of the Invention) In the most preferred embodiment of the present invention, the thermoplastic resin (c) in which the flaky pigment etc. is blended is (i) a thermoplastic resin having a melting point lower than that of the oxygen barrier thermoplastic resin (A); has a softening point, and (ii) has a melting point or softening point lower than the melting point of the moisture-resistant thermoplastic resin (B), or has a melt index higher than that of the resin (B). A blend of this resin (C) with flake pigment, etc. is mixed in a sandwich-like mold between the flow of the oxygen barrier resin melt and the flow of the moisture-resistant melt in a multilayer die. In this state, simultaneous extrusion is carried out. That is, the resin (C) containing the flake pigment is
By satisfying the conditions (i) and (ii), this blend has an extremely low melt viscosity and is in a fluid state in the die, so that the flake pigment is concentrated in the center of the thickness direction. The resin (C) is distributed densely and overlapping in layers in the plane direction, and the resin (C) concentration is extremely high in the areas adjacent to the oxygen barrier resin (A) and the moisture-resistant resin (B). Due to such a distribution structure with a concentration gradient, in this aspect of the present invention, the adhesion between each layer is particularly excellent, and the air bag prevention performance is also particularly excellent. If the moisture-resistant resin (B) and the blend layer resin (C) are the same type of olefin resin, the blend layer resin
As (C), it is recommended to use a moisture-resistant resin whose melt index is at least 1.5 to 10 g/10 min higher than that of (B), preferably 2 to 4 g/10 min higher. Furthermore, the melting point of the ethylene-vinyl alcohol copolymer increases as the content of vinyl alcohol units increases, but from this point of view, the present invention also applies to copolymers whose vinyl alcohol content is within the above-mentioned range. It is particularly suitable for the purpose of Of course, squeeze containers that can be retort sterilized by using a heat-resistant resin are also included within the scope of the present invention. (Example) Example 1 As an oxygen barrier resin layer, ethylene content
30 mol%, vinyl alcohol content 69.7 mol%,
Using an ethylene-vinyl alcohol copolymer (A) with a vinyl acetate content of 0.3 mol% (melting point 183°C),
As a moisture-resistant resin, it has a melting point of 105℃, a melt index (MI) of 0.5g/10min, and a density of 0.91g/ ^cm3 (20
°C) low density polyethylene (B), melting point 102 °C,
Ethylene-vinyl acetate copolymer (C) with vinyl acetate content of 5% by weight, MI 0.5g/10min, density 0.92g/cm ³ (20℃), melting point 116℃, MI 0.4g/10min, density
Medium density polyethylene (D) of 0.93g/cm ³ (20℃), melting point 128℃, MI 0.3g/10min, density 0.95g/cm ³ (20
°C) high-density polyethylene (E), melting point 154 °C,
Ethylene-propylene copolymer (F) with MI1.4g/10min, density 0.90g/cm ³ (20℃) and melting point 163
℃, MI0.7g/10min, density 0.91g/ ^cm3 (20℃)
Polypropylene (G) having a melting point of 102° C. is used as a blend layer interposed between the intermediate layer of the oxygen barrier resin and the inner and outer layers of the moisture-resistant resin.
Blend (H) containing 40 parts by weight of mica flakes with an aspect ratio of 30 to 100 parts by weight of acid-modified low-density polyethylene manufactured by Mitsubishi Yuka, MI2.0g/10min, density 0.926g/cm ³ (20℃) and as a comparative example, acid-modified low-density polyethylene instead of the blend layer. Three types of five-layer containers having the layer structure, layer composition ratio, etc. shown in Table 1 were molded as shown below. It was molded using a machine. Extruder for oxygen barrier resin layer with built-in screw with diameter 40mm and effective length 800mm, diameter 35mm,
An adhesive interlayer press machine equipped with a built-in screw with an effective length of 700 mm and an adapter with two branched melt channels, and a diameter of 65 mm.
Multilayer extrusion machine consisting of an extruder for olefinic resin layers (inner and outer layers) equipped with a built-in screw with an effective length of 700mm and an adapter with a melt channel branched into two, and a die for symmetrical five-layer extrusion. Using a machine, a molten multilayer parison having the layer structure shown in Table 1 was formed, and this parison was sandwiched between molds cooled to 10°C and blow-molded at a blow pressure of 6 kg/cm ^2. A multilayer tube container containing 120 g of content was obtained. Table 1 shows restoring force, moisture permeability, oxygen permeability,
Evaluation results regarding light transmittance and appearance characteristics are shown. As is clear from this table, the Examples are superior to the Comparative Examples in air bag prevention properties, moisture impermeability, etc., and are extremely functional when used as squeeze tube containers. Example 2 The ethylene-vinyl alcohol copolymer (A) described in Example 1 was used as the intermediate oxygen barrier resin layer, and the low-density polyethylene described in Example 1 was used as the inner moisture-resistant resin layer. (B) and ethylene-vinyl acetate copolymer (C) were used as the outer layer, melting point 100℃, MI 1.0g/min, density 0.94g/cm ³
(20°C), using a blend (I) in which 30 parts by weight of mica flakes with an aspect ratio of 30 were blended with 100 parts by weight of maleic anhydride-modified ethylene-vinyl acetate copolymer with a vinyl acetate content of 13% by weight, Using the same molding equipment and molding method as in Example 1, three types and three layers of tube containers containing 100 g of contents were obtained. Restoration power, moisture permeability,
As shown in Table 2, the evaluation results regarding oxygen transmittance, light transmittance, and appearance characteristics indicate that the container is extremely excellent as a squeezing container. The evaluation method was the same as in Example 1. Example 3 An ethylene-vinyl alcohol copolymer (J) with an ethylene content of 40 mol% (melting point 165°C) was used as the oxygen barrier resin for the intermediate layer, and the same as described in Example 1 was used as the moisture-resistant resin for the inner and outer layers. An ethylene-propylene copolymer (F) with an aspect ratio of 30 is used for 100 parts by weight of the ethylene-propylene copolymer (F) as a blend layer interposed between the intermediate layer and the inner and outer layers. A blend (K) containing 50 parts by weight of mica flakes was used, and a melting point of 152°C, an MI of 2.5 g/min, and a density were added between the intermediate layer and the blend layer.
0.905g/ ^cm3 maleic acid modified polypropylene (L)
Using the same method as in Example 1, tube containers containing 120 g of contents and having 4 types and 7 layers were obtained. Restoration power, moisture permeability,
As shown in Table 3, the evaluation results for oxygen transmittance, light transmittance, and appearance characteristics indicate that the container is extremely excellent as a squeezing container. The tube container was filled with 120 c.c. of water and sealed, and retort sterilized at 120°C for 30 minutes without causing any problems. The evaluation method was the same as in Example 1.

【table】

【table】

【table】

【table】 [Brief explanation of the drawing]

Fig. 1 is an external view of the tube package of the present invention, Fig. 2 is a sectional view of the tube package, Fig. 3 is an enlarged cross-sectional view of the multilayer parison wall, Fig. 4-A, Fig. 4-B,
Figure 4-C, Figure 4-D, Figure 4-E, Figure 4-F
The figure is a process diagram showing a method for manufacturing a tube package. DESCRIPTION OF SYMBOLS 1...Tube body, 2...Lid, 3...Extrusion port with screw, 4...Shoulder part, 5...Body part, 6...Oxygen barrier resin layer, 7...Moisture-resistant resin layer, 8... ...Blend layer, 9... Edge portion, 10... Inner view, 1
DESCRIPTION OF SYMBOLS 1... Extruder, 12... Multilayer die, 13... Multilayer parison, 14... Split mold, 15... Cavity, 16... Base insert, 17... Flexible bottle, 18... Cutter, 19... ...bottom, 20
... Edge portion, 21 ... Filling nozzle, 22 ... Contents, 23 ... Heat seal bar.

Claims (1)

[Scope of Claims] 1. A multilayer laminate structure comprising an oxygen barrier thermoplastic resin layer, a moisture-resistant thermoplastic resin layer, and a thermoplastic resin blend layer having a flake pigment or flake filler distributed in layers. A squeeze container with excellent air bag prevention properties. 2. The container according to claim 1 or 2, wherein the oxygen barrier thermoplastic resin layer is made of an ethylene-vinyl alcohol copolymer having a vinyl alcohol content of 40 to 85 mol%. 3. The container according to claim 1, wherein the moisture-resistant thermoplastic resin is an olefin resin. 4. The thermoplastic resin blend layer comprises an acid-modified olefin resin, an olefin resin, or a blend thereof, and 5 to 100 parts by weight of flake pigment or flake filler per 100 parts by weight of the resin. Container as described in Range 1. 5. The container according to claim 1, wherein the flake pigment or filler is mica or flake metal powder. 6. A laminated structure according to claim 1, comprising a multilayered structure in which a moisture-resistant thermoplastic resin layer is provided on both the inner and outer surfaces, a gas barrier thermoplastic resin is provided in the middle, and a blend layer is interposed between both layers. container. 7. The container according to claim 1, wherein the multilayer laminate structure is a coextruded laminate structure. 8. The container according to claim 1, which is in the form of a tube-shaped container. 9. A container according to claim 1 in the form of a flexible bolt. 10 Consists of a multilayer structure including an oxygen barrier thermoplastic resin layer, a moisture-resistant thermoplastic resin layer, and a thermoplastic resin blend layer containing a flake pigment or flake filler, the thermoplastic resin layer containing a flake pigment or a flake filler. The resin (i) has a melting point or softening point lower than the melting point of the oxygen barrier thermoplastic resin, and (ii) has a melting point or softening point lower than the moisture resistant thermoplastic resin, or An airbag having a melt index higher than A squeeze container with excellent prevention properties.