JP2016150949A - Molding and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molding excellent in gas barrier properties to both oxygen and water vapor.MEANS FOR SOLVING THE PROBLEM: The molding is provided that is obtained by molding a blended resin containing PP and EVOH as main components into a film shape or the like. EVOH is dispersed into PP to form a disperse phase. The disperse phase is a layer substantially parallel to a surface direction in at least the vicinity of the surface. A weight ratio of PP and EVOH is 15:85 to 85:15. Oxygen gas is effectively blocked by presence of a layer, and water vapor is effectively blocked by presence of a PP matrix phase.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a molded body and a manufacturing method thereof.

  Various resin films and resin cases are used as packaging materials and containers having excellent gas barrier properties, typically as food packaging materials. However, many resins have a gas barrier property against a specific gas, but have a problem that the gas barrier property is inferior to a gas other than the specific gas. For example, a film of an olefin resin such as polypropylene (hereinafter referred to as “PP”) has an excellent gas barrier property against water vapor but is inferior to a gas barrier property against oxygen. On the other hand, for example, a film of a hydrophilic resin such as an ethylene-vinyl alcohol copolymer (hereinafter referred to as “EVOH”) is excellent in gas barrier properties against oxygen, but is poor in gas barrier properties against water vapor. For this reason, the material excellent in gas barrier property with respect to both oxygen and water vapor | steam is calculated | required.

  On the other hand, conventionally, a resin film having an excellent gas barrier property against oxygen and a plurality of kinds of films such as a resin film having an excellent gas barrier property against water vapor are laminated in two layers or multiple layers to form oxygen and water vapor. In both cases, a material having excellent gas barrier properties has been obtained (see, for example, Patent Document 1). However, the laminated film has a problem that the manufacturing process is complicated and the adhesion between the films is not always good.

  On the other hand, it is considered to blend a resin with excellent gas barrier properties against oxygen and a resin with excellent gas barrier properties against water vapor to obtain a material with excellent gas barrier properties against both oxygen and water vapor. It is done.

JP-A-10-080984

  However, a resin that has excellent gas barrier properties with respect to oxygen and a resin that has excellent gas barrier properties with respect to water vapor can be mixed and melted arbitrarily to blend with both oxygen and water vapor. There is a possibility that the material becomes inferior in gas barrier properties.

  In addition, a resin excellent in gas barrier property against water vapor and a resin excellent in gas barrier property against oxygen do not necessarily have good affinity. A resin obtained by blending these resins may cause a problem in moldability and mechanical properties.

  Then, an object of this invention is to provide the molded object excellent in gas barrier property with respect to both oxygen and water vapor | steam, and its manufacturing method. Furthermore, an object of the present invention is to provide a molded article having excellent gas barrier properties against both oxygen and water vapor and excellent mechanical properties, and a method for producing the same.

  In order to achieve the above-mentioned object, the molded product according to the present invention is made of a blend resin mainly composed of polypropylene (PP) and an ethylene-vinyl alcohol copolymer (EVOH) in a shell shape, a plate shape, a cylindrical shape, or A molded body formed into a film-like shape, wherein the EVOH is dispersed in the PP to form a dispersed phase, and the dispersed phase forms a layer substantially parallel to the surface direction at least in the vicinity of the surface. The weight ratio with EVOH is 15:85 to 85:15.

  In the molded body, the melt flow rate (MFR) at a PP temperature of 200 ° C. and a load of 2.16 kg may be smaller than the EVOH temperature of 200 ° C. and a load of 2.16 kg.

  In the molded body, a weight ratio of the PP to the EVOH is 15:85 to 75:25, and the blend resin may include a compatibilizing agent of 0.5 to 10 phr.

  Further, the method for producing a molded body according to the present invention includes a melt blending step of obtaining a blend resin by melting while shearing PP and EVOH as main components, and the blend resin in a shell shape, a plate shape, a cylindrical shape or a film shape. Forming a molded product into a shape, and extending the molded product in one direction parallel to the surface direction of the molded product and in another direction perpendicular to the one direction and parallel to the surface direction. A weight ratio between the PP and the EVOH in the blend resin may be 15:85 to 85:15.

  Furthermore, the method for producing a molded body according to the present invention includes a melt blending step of obtaining a blend resin by melting while shearing PP and EVOH as main components, and the blend resin in a shell shape, a plate shape, a cylindrical shape, or a film shape. Forming a molded product into a shape, and extending the molded product in one direction parallel to the surface direction of the molded product and in another direction perpendicular to the one direction and parallel to the surface direction. A weight ratio of the PP and EVOH of the blend resin of 15:85 to 75:25, and the blend resin may include a compatibilizer of 0.5 to 10 phr.

  According to the molded body according to the present invention having the above-described configuration, PP and EVOH are molded into a film-like shape, EVOH is dispersed in PP to form a dispersed phase, and the dispersed phase is the surface of the molded body. Since a layer substantially parallel to the direction is formed, oxygen gas is effectively blocked by the presence of the layer, and water vapor is effectively blocked by the presence of the PP matrix phase. For this reason, the molded object which concerns on this invention is excellent in gas barrier property with respect to both oxygen and water vapor | steam.

  Furthermore, the molded body according to the present invention has an elastic modulus, a yield stress, when the weight ratio of PP to EVOH is 15:85 to 75:25 and the compatibilizer is contained in an amount of 0.5 to 10 phr. Since the elongation at break is improved, not only is the gas barrier property excellent against both oxygen and water vapor, but also the mechanical properties are excellent.

The schematic diagram explaining the concept of the form of the molded object which concerns on this invention. It is a X-ray CT photograph of each sample film cross section concerning Experimental Example 1, (a) is sample A-PP ₆₀ EV ₄₀ , (b) is sample A-PP ₆₀ EV ₄₀ with, (c) is sample A-PP. ₈₀ EV ₂₀ , (d) shows Sample A-PP ₈₀ EV ₂₀ with. A SEM photograph of the film section after extracting EVOH from each sample film according to Experimental Example 1, (a) Samples _{A-PP 60 EV} 40 is, (b) the sample _{A-PP 60 EV 40 with,} (c) Represents Sample A-PP ₈₀ EV ₂₀ , and (d) represents Sample A-PP ₈₀ EV ₂₀ with. The graph which shows the oxygen permeation amount of each sample which concerns on Experimental example 2, and the relationship of time. An X-ray CT images viewed Samples _B-PP 60 _{EV 40} according to Experiment 2 obliquely from above of the film, (a) represents the film table surface, (b) is the film middle, (c) Indicates the back surface of the film. A SEM photograph of the film section after extracting EVOH from each sample film according to Experimental Example 2, (a) the sample _{B-PP 90 EV 10, (} b) the sample _{B-PP 70 EV 30, (} c) is Sample B-PP ₆₀ EV ₄₀ is shown. The graph which shows the relationship between 200 degreeC melt viscosity and shear angular velocity of PP and EVOH. 10 is a graph showing the relationship between the oxygen permeation amount and time of each sample according to Experimental Example 3. Graph showing the relationship between the mixing ratio of reduction rate R _P and EVOH of the oxygen in the sample film gas permeability coefficient G _P according to Experimental Examples 2 and 3. The SEM photograph of the film cross section after EVOH extraction from sample B-LvPP ₆₀ EV _{40 which} concerns on Experimental example 4. FIG.

[Molded body]
As shown in FIG. 1, the molded object 2 which concerns on this invention consists of blend resin which has PP and EVOH as a main component. The molded body 2 is formed into a shell shape, a cylindrical shape, a plate shape, or a film shape.

  The molded body 2 has a sea-island phase structure in which the EVOH phase 4 is an island (dispersed phase) and the PP matrix phase 6 is the sea. Further, since the blend resin is stretched when the molded body 2 is molded, the EVOH phase 4 forms a thin plate-like layer 10. Stretching means that a force that causes the molded product to extend in a predetermined direction is applied to the molded product.

  The surface direction of the layer 10 is substantially parallel to the surface direction 8 of the molded body 2, and at least one layer 10 exists in the vicinity of the surface of the molded body 2. It is preferable that a plurality of layers 10 exist and are laminated in the thickness direction 12 of the molded body 2 as shown in FIG. 1 to form a multilayer structure. That is, in the molded body 2, EVOH is dispersed in PP to form a dispersed phase, and this dispersed phase forms a layer 10 substantially parallel to the surface direction 8 of the molded body 2 at least near the surface of the molded body 2.

  The thickness t of the layer 10 is 1 to 30 μm, and the vertical width and width are preferably 2 to 100 times the thickness t. The shape of the EVOH phase 4 viewed from above is a substantially rounded square, a substantially oval, a substantially oval, a substantially oval, a substantially spindle, or a plurality of these having a surface direction of 8 in part. The shape is suitable for

  The mixing ratio of PP and EVOH in the molded body 2 is in the range of 15:85 to 85:15 by weight. If the PP ratio is small below this mixing ratio, the amount of the PP matrix phase 6 interposed between the adjacent layers 10 in the thickness direction 12 of the molded body 2 is insufficient, and the ability to block water vapor is insufficient. . If the PP ratio increases above this mixing ratio, the amount of the layer 10 is insufficient and the ability to block oxygen is insufficient.

  With the above configuration, in the molded body 2, oxygen gas is effectively blocked by the presence of the layer 10, and water vapor is effectively blocked by the presence of the PP matrix phase 6.

  For this reason, the molded body 2 can reduce oxygen gas permeation by 50% or more compared to the PP film, and can reduce water vapor permeation by 50% or more compared to the EVOH film. If the conditions such as the blending ratio of PP and EVOH are further appropriately selected, the molded body 2 reduces oxygen gas permeation by 90% or more compared to the PP film, and 80 permeation of water vapor compared to the EVOH film. % Or more can be reduced. If the conditions such as the blending ratio of PP and EVOH are further appropriately selected, the molded body 2 reduces oxygen gas permeation by 95% or more compared to the PP film, and water vapor permeation compared to the EVOH film. It can be reduced by 80% or more.

  Therefore, according to this invention, the molded object 2 excellent in gas barrier property with respect to both oxygen and water vapor | steam can be provided.

  In the molded body 2, the melt flow rate (hereinafter referred to as “MFR”) at a PP temperature of 200 ° C. and a load of 2.16 kg is preferably smaller than the MFR at an EVOH temperature of 200 ° C. and a load of 2.16 kg. In the molded body 2, the MFR at a PP temperature of 200 ° C. and a load of 2.16 kg is more preferably 1/10 to 1/2 of the MFR at an EVOH temperature of 200 ° C. and a load of 2.16 kg. In addition, the above-mentioned MFR value is a value measured by a test method based on JIS K 7210.

  If the MFR of PP is smaller than the MFR of EVOH, there is a high possibility that the EVOH phase will have greater fluidity or softer than the PP phase during stretching. In such a case, when the blend resin is stretched, the EVOH phase 4 tends to become the thin plate-like layer 10. The presence of the thin plate-like layer 10 makes it difficult for oxygen gas to permeate the molded body 2, so that the molded body 2 tends to exhibit performance with excellent gas barrier properties against oxygen.

  The blend resin used as the raw material of the molded body 2 contains substantially no compatibilizing agent, but may contain a compatibilizing agent of PP and EVOH. The compatibilizer is a polymer substance that lowers the interfacial tension between two types of polymers in the blend resin, relaxes the difference in properties, and stabilizes the phase separation structure.

  Examples of the compatibilizing agent include hydrocarbon polymers having a polar group. Examples of polar groups include sulfur-containing groups such as sulfonic acid groups, sulfenic acid groups, and sulfinic acid groups, and carbonyl groups such as hydroxyl groups, epoxy groups, ketone groups, ester groups, aldehyde groups, carboxyl groups, and acid anhydride groups. Nitrogen-containing groups such as group-containing groups, glycidyl groups, nitro groups, amide groups, urea groups, isocyanate groups, phosphorus-containing groups such as phosphonic acid ester groups, phosphinic acid ester groups, boronic acid groups, boronic acid ester groups, boron Examples thereof include boron-containing groups such as acid anhydride groups and boronate groups.

  Specific examples of the compatibilizer include maleic acid-modified PP (hereinafter referred to as “PP-g-MAH”). PP-g-MAH is a polymer obtained by graft polymerization of maleic anhydride (hereinafter referred to as “MAH”) to a PP chain. In the blend resin, MAH which is an acid anhydride reacts with the hydrophilic group of EVOH, and the PP chain of PP-g-MAH interacts with the matrix PP having a structure similar to the PP chain. The PP / EVOH blend system is to some extent compatible.

  If the concentration of the compatibilizing agent contained in the blend resin is too high, the EVOH phase is finely dispersed, which prevents the formation of the layer 10. In order to avoid fine dispersion of the EVOH phase, it is preferable to add the compatibilizer so that the compatibilizer is contained in the blend resin at a concentration in the range of 0.5 to 10 phr.

  When the blend resin contains a compatibilizing agent, the mixing ratio of PP and EVOH is preferably 15:85 to 75:25 in terms of weight ratio in order to form a layer structure such as the EVOH layer 10. It is further preferable that the mixing ratio of PP and EVOH is 25:75 to 75:25 by weight to reduce the permeability of oxygen gas. It is most preferable that the mixing ratio of PP and EVOH is 35:65 to 75:25 by weight to reduce the water vapor permeability.

  As described above, when the blend resin contains a compatibilizing agent, the fragile mechanical characteristics of the molded body 2 can be improved. That is, when the blend resin includes a compatibilizing agent, the elastic modulus, yield stress, and elongation at break of the molded body 2 are improved as compared with the case where the compatibilizing agent is not included. Therefore, according to this invention, the molded object 2 which was excellent in gas barrier property with respect to both oxygen and water vapor | steam, and was excellent in the mechanical characteristic can be provided.

  A third component other than PP and EVOH may be added to the blend resin in a range of 10 phr or less. For example, ordinary additives for resins such as pigments and stabilizers may be added within the range of the mixing ratio of ordinary additives.

[Method for producing molded article]
Molded body 2 is a melt blending step in which PP and EVOH are sheared as main components to obtain a blend resin by melting and molding the blend resin into a shell, plate, cylinder, or film to form a molded product And a stretching step of stretching the molded product in one direction parallel to the surface direction of the molded product and in another direction perpendicular to the one direction and parallel to the surface direction. It is preferably produced by a molding method having a weight ratio with EVOH of 15:85 to 85:15.

  In the melt blending process, PP and EVOH are sheared and melted as main components to obtain a blend resin, and EVOH is dispersed spherically in PP in the melted blend resin to form a dispersed phase. In the molding step, the melted blended resin is molded as it is or after being cooled and then molded into a film shape or the like in a molten state to form a molten molded product. In the stretching step, the EVOH phase is melted by stretching the molded product in a molten state in one direction parallel to the surface direction of the molded product and in another direction perpendicular to the one direction and parallel to the surface direction. The layer 10 is formed by extending in the surface direction of the shaped product and flattening.

  Therefore, according to the manufacturing method of the molded body 2 according to the present invention, when the weight ratio of PP and EVOH of the blend resin is 15:85 to 85:15, the layer shown in FIG. A structure is formed, and after the stretching step, a molded body 2 having excellent gas barrier properties against both oxygen and water vapor can be obtained. In this production method, the blend resin is substantially free of a compatibilizing agent.

  Alternatively, the molded body 2 includes a melt blending step in which PP and EVOH are sheared as main components and melted to obtain a blend resin, and the blend resin is molded into a shell shape, a plate shape, a cylindrical shape, or a film shape, A molding step, and a stretching step of stretching the molded product in one direction parallel to the surface direction of the molded product and in another direction perpendicular to the one direction and parallel to the surface direction. The weight ratio of PP to EVOH is preferably 15:85 to 75:25, and the blend resin is preferably produced by a molding method containing a compatibilizing agent in an amount of 0.5 to 10 phr.

  In the method for producing the molded body 2 according to the present invention, when the weight ratio of PP and EVOH of the blend resin is 15:85 to 75:25, and the blend resin contains a compatibilizer of 0.5 to 10 phr, The obtained molded body 2 has excellent gas barrier properties against both oxygen and water vapor, and has excellent mechanical properties.

  The forming step and the stretching step may be performed simultaneously or continuously. The melt blending step, the forming step, and the stretching step may be performed simultaneously or sequentially.

  The melt viscosity of PP measured under the condition of shear rate corresponding to the shear rate of the blend resin in the melt blending process and the temperature condition corresponding to the melt temperature of the blend resin in the melt blending process is the same as that of the PP. It is preferably greater than or equal to the melt viscosity of EVOH measured below.

  When the melt viscosity at the melt rate at the melt blending step of PP and the melt viscosity at the melt temperature of EVOH is smaller than the melt viscosity at the shear rate and melt temperature of EVOH, the EVOH phase (island phase) is finely dispersed in the molded product in the molding step. The diameter of each EVOH phase becomes smaller than about 5 μm, for example. In this case, it is difficult to form the EVOH layer 10 by stretching in the stretching process. In this case, it is considered that oxygen gas passes through the PP matrix phase 6 preferentially while avoiding the EVOH phase 4 which is difficult to permeate in the molded body 2.

  Conversely, if the melt viscosity at the melt rate at the melt blending step of PP is greater than the melt viscosity at the melt rate at the EVOH, the individual EVOH phase (island phase) in the molding during the molding step. Is relatively large, for example, 10 μm or more. In this case, the EVOH layer 10 having a relatively large area is formed by stretching in the stretching step. Thereby, it is considered that oxygen gas is effectively blocked in the molded body 2.

  In the stretching step, EVOH phases adjacent to each other may be combined in the surface direction during stretching to form a wide layer 10. The EVOH layer 10 is most preferably laminated in multiple layers in the thickness direction of the molded body 2 to form a multilayer structure. At this time, PP exists in each of the layers 7 facing the stacked EVOH layer 10. That is, the EVOH layer 10 is laminated via PP and exists in a multilayered form. When most of the EVOH phases contained in the molded product before stretching are finely dispersed with the individual phase diameters of 5 μm or less, it is difficult to form an effective layer 10 for blocking oxygen gas.

  The MFR at a PP temperature of 200 ° C. and a load of 2.16 kg is preferably smaller than the MFR at an EVOH temperature of 200 ° C. and a load of 2.16 kg in order to form the layer 10 during stretching. The MFR at a PP temperature of 200 ° C. and a load of 2.16 kg is more preferably 1/10 to 1/2 of the MFR at an EVOH temperature of 200 ° C. and a load of 2.16 kg in order to form the layer 10 during stretching. .

  Alternatively, in the method of manufacturing the molded body 2, the molding step is to form the molded blended resin as it is or after cooling and solidifying, and then molding into a shell, cylinder, plate, or film (film) shape. The stretching step preferably stretches the molded product in a softened or molten state in one direction parallel to the surface direction of the molded product and in another direction perpendicular to the one direction and parallel to the surface direction. It may be. In this case, the phase of EVOH is extended in the surface direction of the molded product and flattened to form the layer 10.

  Even when the molded product is stretched in a softened or molten state in the stretching step, the phases of EVOH adjacent to each other may be combined in the surface direction during stretching to form a wide layer 10. Also in this case, it is most preferable that the EVOH layers 10 are laminated in multiple layers in the thickness direction 12 of the molded body 2 to form a multilayer structure. At this time, PP exists in each layer 7 facing the layer 10 of the stacked EVOH. That is, the EVOH layer 10 is laminated through PP and exists in a multilayered form. Also in this case, if the diameter of each EVOH phase formed in the melt before stretching is finely dispersed to 5 μm or less, it is difficult to form the layer 10 effective in blocking oxygen gas.

  When the molded product is stretched in a softened or molten state in the stretching step, the stretching ratio is preferably 1.5 to 15 times in both directions. If the draw ratio is less than 1.5 times, there may be a portion where EVOH phase flattening is incomplete. If it exceeds 15 times, stretching may be unstable, or the EVOH phase may become extremely thin or broken. In order to prevent these phenomena, the draw ratio is more preferably 2 to 10 times in both directions. Stretching is preferably performed in a molten state or in a state where the molded product is softened from the normal temperature state at a temperature higher than the normal temperature state in order to develop a layer structure.

  As a method of stretching a molded product in a softened state in one direction parallel to the surface direction of the molded product and in another direction perpendicular to the one direction and parallel to the surface direction, for example, film formation by an inflation method And production of shells (such as containers) by blow molding. The inflation method is a film-forming method in which a compressed air is blown into the inside of a tube obtained by extruding a blend resin in a molten state from a ring die to expand the tube. When the tube expands, it is parallel to the surface direction of the film. The film is stretched in one direction and in another direction orthogonal to the one direction and parallel to the surface direction. In blow molding, stretching is performed by an expansion mechanism similar to that of the inflation method.

  As another example of a method of stretching a molded product in a molten state in one direction parallel to the surface direction of the molded product and another direction perpendicular to the one direction and parallel to the surface direction, a press method is used as another example. And a method for producing a film or shell (a container or the like). In the press method, PP and EVOH are melted while shearing with PPOH as a main component to obtain a blend resin, the blend resin is once cooled to form chips, and the chips are arranged in a plane in a predetermined mold and melted. The compact 2 is obtained by hot pressing. By hot pressing, the chip becomes a molded product, and the molded product is stretched by a force generated in the molded product in a direction orthogonal to the pressing direction. If the melt viscosity of PP at the temperature of the melt blending process is higher than the melt viscosity of EVOH at this temperature, the EVOH phase tends to flow into a layer by this stretching and stratify, which contributes to the improvement of oxygen gas barrier properties. .

  Further, as another example of a method of extending a molded product in one direction parallel to the surface direction of the molded product and in another direction orthogonal to the one direction and parallel to the surface direction, Examples thereof include a method of biaxially stretching a film-like molded product obtained by extruding a melted blend resin from a slit die.

  The following experimental examples 1 to 4 including examples will explain in detail the phenomenon that is the basis of the present invention and the configuration and effects of the molded body and the manufacturing method thereof according to the present invention.

[Experiment 1]
[Method for Producing Sample According to Experimental Example 1]
As PP, Isotactic-PP: F113-G (manufactured by Prime Polymer Co., Ltd.) was prepared. Moreover, as EVOH, J-E105B (made by Kuraray Co., Ltd.) was prepared. Table 1 shows the characteristic values of the prepared PP and EVOH. In addition, MFR measurement of PP and EVOH was performed using IMC-1540 (manufactured by Imoto Seisakusho Co., Ltd.) under a condition in which a load of 2.16 kg was applied to a resin having a temperature of 200 ° C. in accordance with JIS K 7210.

As a compatibilizer, PP-g-MAH: P ₇₇ M _2.0 (manufactured by Kayaku Akzo Corporation) was prepared. The characteristic values of the prepared compatibilizer are shown in Table 2.

  Next, a blend resin was prepared by melt blending using KZW 15HG (manufactured by Technobell Co., Ltd.) as a twin screw extruder. The prepared virgin resin raw material was dry blended in advance and then charged into a twin screw extruder. The blend resin was prepared in an air atmosphere under conditions of a kneading temperature of 200 ° C., a screw rotation speed of 250 rpm, and a discharge amount of the blend resin of 30 g / min, and the discharged blend resin was water-cooled.

When preparing the blend resin, the prepared PP and EVOH were kneaded so that the mixing ratio (% by weight) was 60:40 or 80:20. Furthermore, when a compatibilizing agent is included in the blend resin, the compatibilizing agent is added so that the compatibilizing agent occupies 5 phr with respect to the total amount of the blend resin, and then the compatibilizing agent is kneaded with PP and EVOH. It was. As shown in Table 3, resin A-PP ₆₀ EV ₄₀ , resin A-PP ₆₀ EV ₄₀ with, resin A-PP ₈₀ EV ₂₀ , and resin A-PP ₈₀ EV ₂₀ with were prepared as blend resins. The “with” here indicates that the blend resin contains a compatibilizing agent.

  After preparing the blend resins shown in Table 3, each sample film was produced using the blend resin by an inflation method with TYPE EAW-50 (manufactured by Modern Machinery Co., Ltd.) as an extrusion blow molding machine. The sample film was manufactured under an air atmosphere at a melting temperature of 210 ° C., a screw rotation speed of 70 rpm, a stretching ratio of 4 times in the MD direction (flow direction), and a stretching ratio of 2 times in the TD direction (direction perpendicular to the MD direction). The subsequent molding was performed under the condition of air cooling.

About the obtained sample film, what was manufactured using resin A-PP ₆₀ EV ₄₀ is set to sample A-PP ₆₀ EV _40, and what was manufactured using resin A-PP ₆₀ EV ₄₀ with is sample A-PP _60. What was manufactured using resin A-PP ₈₀ EV ₂₀ as sample EV ₄₀ with sample A-PP ₈₀ EV ₂₀ and sample manufactured using resin A-PP ₈₀ EV ₂₀ with sample A-PP ₈₀ EV ₂₀ It was with. Moreover, as a comparison object, PP film A manufactured using PP and EVOH film A manufactured using EVOH were obtained by an inflation method under the same conditions.

[Tensile test in Experimental Example 1]
The sample film was cut into a dumbbell shape and used as a test piece. The test piece had a total length of 60 mm, a central portion length of 10 mm, and a central portion width of 4 mm. Using EZ-Test (manufactured by Shimadzu Corporation), the test piece was subjected to a constant-speed tensile test under conditions of a distance between chucks of 10 mm and a pulling speed of 20 mm / min.

Table 4 shows the data of the elastic modulus, yield stress, and elongation at break of each sample film obtained by the tensile test.

  As is clear from Table 4, the samples containing the compatibilizer in the blend resin had higher values of elastic modulus, yield stress, and elongation at break than the samples containing no compatibilizer. That is, in the sample in which the compatibilizer is included in the blend resin, the fragile mechanical properties are improved.

[Measurement of gas permeation amount in Experimental Example 1]
The sample film was cut into a circle with a diameter of 22 mm to obtain a test piece. The oxygen permeation amount and water vapor permeation amount of the test piece were measured by GTR-10XCT, 2700T (manufactured by GTR Corporation).

The oxygen permeation amount was measured by a differential pressure method using helium gas as a carrier gas under the conditions of a measurement temperature of 23 ° C., a measurement effective area of 15.2 cm ² , a sampling interval of 5 or 10 minutes, and a sampling frequency of 2 times. From the data obtained by the measurement, the oxygen permeability PO ₂ was calculated by the following formula 1 in accordance with JIS K 7126-1. The numerical value of PO ₂ is standardized with a film thickness of 20 μm.

(Dv-Db): Transmission amount (cm ³ )
k: apparatus coefficient A: effective measurement area (0.00152 m ² )
t: Measurement time (h)
ΔP: partial pressure of high-pressure side gas (mmHg)
T: Film thickness (μm)

Furthermore, the value of the PO ₂ of the PP film A was compared, based on the value of the PO ₂ of the sample film was calculated value of _{R O2} by Equation 2 below. The calculated value of the RO _2, and the value of the reduction rate _{R P} of PO ₂ for PP films.
In Equation 2, _{P X} represents a gas permeability PO _2. Note that in Equation 2 is shown in suffix superscript types of samples of interest to P _X.

And oxygen permeability PO ₂ of each sample film, showing a reduction ratio _{R P} of the oxygen permeability PO ₂ for PP film are shown in Table 5.

As shown in Table 5, with respect to oxygen gas, the sample _A-PP 60 _{EV 40,} in Sample _{A-PP 60} EV 40 with, a very high gas barrier properties that _{R P} is 95% or more is exhibited. To oxygen gas, in Sample _A-PP 80 _{EV 20,} high gas barrier properties that _{R P} is 90% or more is exhibited. To oxygen gas, in Sample _{A-PP 80} EV 20 with, its _{R P} is 30.1%, high gas barrier property as compared with PP film A was exhibited.

The water vapor transmission amount was measured by a differential pressure method using helium gas as a carrier gas under the conditions of a measurement temperature of 40 ° C., a set humidity of 85% RH or more, a sampling interval of 1 hour, and a sampling frequency of 1 time. From the data obtained by the measurement, the water vapor permeability PH ₂ O was calculated by the following mathematical formula 3. The numerical value of PH ₂ O is standardized with a film thickness of 20 μm.

q: Transmission amount (cm ³ )
k ′: device coefficient A: effective measurement area (0.00152 m ² )
t: Measurement time (min)
T: Film thickness (μm)

Furthermore, the value of the PH ₂ O of the EVOH film A was compared, based on the value of the PH ₂ O of sample film was calculated value of _{R H2 O} by Equation 4 below. The value of the calculated _{R H2 O,} and the value of the reduction rate _{R P} of PH ₂ O for EVOH film.
In Equation 4, _{P X} represents a gas permeability PH ₂ O. Note that in Equation 4, are indicated by the suffix superscript a type of sample of interest to P _X.

And water vapor permeability PH ₂ O of each sample film, the reduction ratio _{R P} of the water vapor transmission rate PH ₂ O for EVOH films are shown in Table 6.

As shown in Table 6, to water vapor, the sample _{A-PP 60} EV 40 with, in Sample _A-PP 80 _{EV 20,} high gas barrier properties that _{R P} is 80% or more is exhibited. To water vapor, the sample _A-PP 60 _{EV 40,} in Sample _{A-PP 80} EV 20 with, gas barrier properties that _{R P} is 50% or more is exhibited.

[Structural observation in Experimental Example 1]
In order to observe the three-dimensional morphology of the EVOH dispersed phase in the sample film, the sample was subjected to computer tomography (hereinafter referred to as “X-ray CT”) with X-rays. In order to perform X-ray CT, a specimen having a length of 5 mm, a width of 2 mm, and a thickness of about 0.3 mm was cut from a sample film having a thickness of 0.3 mm to obtain a test piece. The test piece was subjected to X-ray CT using ELEX-M345 (BEAMSENSE) under a tube voltage of 70 kV. X-ray CT photographs were edited and observed using image editing software 3DView.

As a result of observing the X-ray CT photograph, sample A-PP ₆₀ EV ₄₀ shown in FIG. 2 (a), sample A-PP ₆₀ EV ₄₀ with shown in FIG. 2 (b), sample A- shown in FIG. 2 (c). In PP ₈₀ EV ₂₀ , a layer of EVOH was confirmed in the cross section. On the other hand, in the sample A-PP ₈₀ EV ₂₀ with shown in FIG. 2 (d), an EVOH layer was not confirmed in the cross section.

  In addition to the X-ray CT, the morphology of the sample was observed with a scanning electron microscope (hereinafter referred to as “SEM”). In order to observe with an SEM, a sample film having a thickness of 0.3 mm immersed in liquid nitrogen to be cryogenic was broken. Thereafter, dimethyl sulfoxide adjusted to 50 ° C. was permeated into the sample fracture surface for 20 minutes, and a test piece was prepared by dissolving only the EVOH phase in the fracture surface. After coating the test piece by platinum vapor deposition, the test piece coated in a high vacuum atmosphere was photographed with SEM using S-3200N (manufactured by Hitachi, Ltd.) as an SEM under the condition of an acceleration voltage of 15 kV.

As a result of observing the SEM photograph of the test piece, the sample A-PP ₆₀ EV ₄₀ shown in FIG. 3A, the sample A-PP ₆₀ EV ₄₀ with shown in FIG. 3B, and the sample A shown in FIG. In -PP ₈₀ EV ₂₀ , a layered structure was confirmed in the cross section. On the other hand, in the sample A-PP ₈₀ EV ₂₀ with shown in FIG. 3D, it was confirmed that the EVOH phase was finely dispersed. According to the observation results of the X-ray CT photograph and the SEM photograph, in the sample A-PP ₆₀ EV ₄₀ , the sample A-PP ₆₀ EV ₄₀ with and the sample A-PP ₈₀ EV ₂₀ , a multilayer structure of the EVOH phase is formed, and the sample A- PP ₈₀ EV ₂₀ with indicates that the EVOH phase is uniformly dispersed.

Based on the results of structural observation, the difference in the structure of each sample is considered. Since PP and EVOH are incompatible, it is considered that in resin A-PP ₆₀ EV ₄₀ and resin A-PP ₈₀ EV ₂₀ , which do not contain a compatibilizing agent, PP was present as a matrix and EVOH as a dispersed phase in the molten state. It is done. When the film is prepared while performing the stretching treatment in this state, the EVOH phase spreads like a plate, and it is considered that a multilayer structure is formed in the sample film.

On the other hand, the resin A-PP ₈₀ EV ₂₀ with contains a compatibilizing agent, and the EVOH phase is finely dispersed by compatibilization of PP and EVOH. It is thought that it was uniformly dispersed in the sample film. However, in the sample A-PP ₆₀ EV ₄₀ with, a multilayer structure was maintained despite containing the compatibilizer. This is because the EVOH mixing ratio is as high as 40%, so that the EVOH phase was compatibilized but was not finely dispersed.

From the results of the structural observation and the gas permeation amount measurement results, the sample A-PP ₆₀ EV ₄₀ , the sample A-PP ₆₀ EV ₄₀ with, and the sample A-PP ₈₀ EV ₂₀ have extremely high gas barrier properties against oxygen gas. It is considered that the reason why is exhibited is the formation of a multilayer structure in the film. In gas permeation, gas has a property of permeating from a place where it easily permeates (large free volume). When a multilayer structure is formed in a film, layers of PP and EVOH are repeatedly provided as in a conventional laminate material, so that oxygen gas is prevented from permeation by a layer of EVOH having a small free volume, and oxygen permeability PO ₂ Is thought to have been greatly reduced.

On the other hand, in the sample A-PP ₈₀ EV ₂₀ with, since the EVOH phase was finely dispersed, it is considered that the oxygen gas preferentially permeated the PP matrix phase having a large free volume and easily permeating, avoiding the EVOH phase that is difficult to permeate. Therefore, it was suggested that the gas barrier property in the sample film in which the EVOH phase is uniformly dispersed is higher than that of the PP film, but is lower than that of the sample film having a multilayer structure.

[Experiment 2]
[Method for Producing Sample According to Experimental Example 2]
As resin materials, PP and EVOH similar to those prepared in Experimental Example 1 were prepared. Next, using a LABOPLASTOMILL 50M (manufactured by Toyo Seiki Co., Ltd.) as a kneader, a blend resin was prepared by melt blending. The prepared virgin resin raw material was dry blended in advance and then charged into a kneader. The blended resin was prepared in an air atmosphere at a kneading temperature of 200 ° C. under a stirring rate of 200 rpm for 2 minutes and then at a stirring rate of 50 rpm for 3 minutes. The blended resin after kneading was pulverized using a pulverizer (strong rotary cutter mill 1005 manufactured by Yoshida Seisakusho Co., Ltd.) to obtain a pulverized sample of about 5 mm square.

In preparing the blend resin, the prepared PP and EVOH are kneaded so that the mixing ratio (% by weight) is 90:10, 80:20, 70:30, 60:40, or 40:60. I let you. No compatibilizer was added to the blend resin according to Experimental Example 2. As shown in Table 7, resin B-PP ₉₀ EV ₁₀ , resin B-PP ₈₀ EV ₂₀ , resin B-PP ₇₀ EV ₃₀ , resin B-PP ₆₀ EV ₄₀ , resin B-PP ₄₀ EV ₆₀ are blended resins. Prepared.

  After preparing the blend resin shown in Table 7, each sample film was manufactured using the blend resin by MH-10 (manufactured by Imoto Seisakusho Co., Ltd.). As an operation, an aluminum plate (200 mm × 200 mm × 1 mm), a fluororesin film, an aluminum mold frame filled with a blend resin, a fluororesin film, and an aluminum plate were sandwiched in this order, and melt pressure molding was performed. . Immediately after molding, it was quenched in ice water. The filling amount of the blend resin was about 1.2 times larger than the volume of the aluminum mold. Each blended resin in a pulverized state was pressurized and melted and deformed by extending in a direction perpendicular to the pressurizing direction during melt press molding.

  For sample films for constant-speed tensile tests and differential scanning calorimetry sample films, the pressing operation was performed under the conditions of a melting temperature of 200 ° C., a gauge pressure of 10 MPa, and a mold size of 100 mm × 100 mm × 0.3 mm. After performing pressureless melting for 1.5 minutes, pressure was released for 1 minute, pressure was applied for 1 minute, and the molded product was rapidly cooled in water to produce a sample film. The sample film for gas permeability measurement was subjected to pressureless melting for 1.5 minutes as a pressing operation under the conditions of a melting temperature of 200 ° C., a gauge pressure of 14 to 16 MPa, and no mold, and then the pressure was released by 1 Then, pressurization was performed for 1 minute, and the molded product was rapidly cooled in water to produce a sample film.

About the obtained sample film, what was manufactured using resin B-PP ₉₀ EV ₁₀ was used as sample B-PP ₉₀ EV _10, and what was manufactured using resin B-PP ₈₀ EV ₂₀ was used as sample B-PP ₈₀ EV. and _20, those produced by using the resin _B-PP 70 _{EV 30} as sample _B-PP 70 _{EV 30,} those produced by using the resin _B-PP 60 _{EV 40} as sample _B-PP 60 _{EV 40,} resin A sample produced using B-PP ₄₀ EV ₆₀ was designated as Sample B-PP ₄₀ EV ₆₀ . Moreover, the PPOH film B manufactured using PP and EVOH film B manufactured using EVOH with the same pressurization method as a comparison object were obtained.

[Tensile test in Experimental Example 2]
In Experimental Example 2, a tensile test was performed as in Experimental Example 1. Table 8 shows the elastic modulus, yield stress, elongation at break, and tensile strength of each sample film obtained from the stress-strain curve.

[Measurement of gas permeation amount in Experimental Example 2]
In Experimental Example 2, the gas permeation amount of oxygen was measured using the same apparatus as in Experimental Example 1 under the same measurement conditions. As shown in FIG. 4, it was shown that each sample according to Experimental Example 2 has a smaller oxygen gas permeation amount as the mixing ratio of EVOH in the blend resin increases.

Further, for each sample according to Experimental Example 2, an oxygen gas permeation coefficient _GP was calculated from the measurement result of the oxygen gas permeation amount according to the following Equation 5. In addition, the numerical value of _GP was converted with the film thickness of 20 μm.
A: Measurement effective area (0.005 m ² )
α: slope of graph in FIG. 4: gas pressure (1 atm)
L: Film thickness (μm)

Furthermore, the value of G _P of PP film B which was compared, based on the value of G _P of the sample film by Equation 6 below, and calculate the value of the reduction rate R _P of G _P for PP film.
G _PP ^PP : Gas permeability coefficient of PP film G _P ^sample : Gas permeability coefficient of each sample film

In each sample film shows an oxygen gas permeability coefficient G _P, the reduction ratio R _P of oxygen gas permeability G _P for PP film are shown in Table 9.

As shown in Table 9, to the oxygen gas, the sample _B-PP 60 _{EV 40,} in Sample _B-PP 40 _{EV 60,} very high gas barrier properties that _{R P} is 95% or more is exhibited. Samples _B-PP 80 _{EV 20,} in Sample _B-PP 70 _{EV 30,} high gas barrier properties that _{R P} is 50% or more is exhibited. To oxygen gas, in Sample _B-PP 90 _{EV 10,} the _{R P} is 28.2%, high gas barrier property as compared with PP film B is exerted.

[Structural observation in Experimental Example 2]
In Experimental Example 2, X-ray CT was performed on the sample B-PP ₆₀ EV ₄₀ by the same method as in Experimental Example 1. According to the X-ray CT, it is possible to take an image without destroying the internal structure of the sample by using the difference in the X-ray absorption coefficient of the substance. In the X-ray CT photograph, the EVOH phase has high brightness on the film front side surface shown in FIG. 5 (a), the film middle layer shown in FIG. 5 (b), and the film back side surface shown in FIG. 5 (c). It was displayed. As a result of observing the X-ray CT photograph, the presence of a dispersed layer extending in parallel with the surface direction was found in the vicinity of the front and back surfaces. However, in the middle layer of the film, a dispersed phase spreading in parallel with the surface direction could not be found.

In Experimental Example 2, a sample was photographed with an SEM in the same manner as in Experimental Example 1. As a result of observing the SEM photograph, as shown in FIGS. 6A, 6B, and 6C, in each sample according to Experimental Example 2 (each sample not including the compatibilizer), the EVOH mixing ratio increases. It was confirmed that the EVOH dispersed phase became large and its shape changed to a flat shape. In particular, in the sample B-PP ₆₀ EV ₄₀ in which the EVOH mixing ratio is 40% by weight as shown in FIG. According to the observation results of X-ray CT photographs and SEM photographs, the EVOH dispersed phase may have a unique morphology that spreads in a layer near the film surface in a sample obtained by forming a blend resin mixed with PP and EVOH into a film shape. confirmed.

[Viscosity Measurement in Experimental Example 2]
Using CVO-100 (manufactured by Bohlin Instruments) as a rheometer, the melt viscosity of PP or EVOH of the prepared resin raw material was measured. The prepared PP or EVOH is put into a rheometer, and a resin is used in a stress control method within a disk-shaped frame with a diameter of 25 mm under the conditions of a set temperature range of 180 to 220 ° C, a step temperature of 10 ° C, and a frequency range of 0.1 to 20 Hz. The melt viscosity of the raw material was measured. In the measurement of the melt viscosity, the gap setting was calculated under the condition that the sample piece thickness was −100 μm, and the measured value of the melt viscosity was obtained.

  When the relationship between the melt viscosity of PP and EVOH at 200 ° C. and the shear angular velocity was examined by the measured values when using a rheometer, the results shown in FIG. 7 were obtained. In FIG. 7, η ′ (Pa · s) represents the dynamic viscosity (G ″ / ω), and ω (rad · s) represents the shear angular velocity. G ″ represents a loss elastic modulus. Further, the shear angular velocity when kneaded for sample preparation is about 0.7 in log ω. For this reason, FIG. 7 shows that the viscosity of PP during kneading was greater than that of EVOH.

In Experimental Example 1, the same resin raw material as in Experimental Example 2 is used. Therefore, according to the relationship between the melt viscosity of PP and EVOH at a temperature of 200 ° C. shown in FIG. 7 and the shear rate, the melt viscosity of PP is EVOH at the shear rate (50 rpm) at the blending operation (kneading) in Experimental Example 1. Is estimated to be greater than the melt viscosity of This is considered to be advantageous in that a flat EVOH layer is formed in the sample, and the oxygen permeability PO _{2 of the} sample is considered to be reduced.

  In Experimental Example 2, it is presumed that the dispersed phase of EVOH was flattened by pressing during film preparation. When the EVOH melt viscosity is smaller than the PP melt viscosity during pressing, the EVOH phase is preferentially deformed and flattened. Therefore, it is considered that the EVOH dispersed phase tends to flatten. . On the other hand, when the EVOH melt viscosity is larger than the PP melt viscosity during pressing, the PP phase preferentially changes, and it is thought that flattening of the EVOH dispersed phase is unlikely to occur.

[Experiment 3]
[Method for Producing Sample According to Experimental Example 3]
As the resin raw material, the same PP, EVOH, and compatibilizer as those prepared in Experimental Example 1 were prepared. Next, after adding the compatibilizer so that the compatibilizer occupies 5 phr with respect to the total amount of the blend resin, the apparatus similar to Experimental Example 2 except that the compatibilizer was kneaded with PP and EVOH, A blended resin was prepared under the operation and preparation conditions.

As blend resins, resin B-PP ₉₀ EV ₁₀ with, resin B-PP ₈₀ EV ₂₀ with, resin B-PP ₇₀ EV ₃₀ with, resin B-PP ₆₀ EV ₄₀ with, resin B-PP ₄₀ EV shown in Table 10 are used. ₆₀ with was prepared.

After preparation of the blend resin shown in Table 10, a sample film was produced under the same apparatus, operation and production conditions as in Experimental Example 2. About the obtained sample film, what was manufactured using resin B-PP ₉₀ EV ₁₀ with was used as sample B-PP ₉₀ EV ₁₀ with, and what was manufactured using resin B-PP ₈₀ EV ₂₀ with sample B- PP ₈₀ EV ₂₀ with a resin B-PP ₇₀ EV ₃₀ with a sample B-PP ₇₀ EV ₃₀ with a resin B-PP ₆₀ EV ₄₀ with a sample B-PP ₇₀ EV ₃₀ with PP ₆₀ EV ₄₀ with was used, and a sample produced using the resin B-PP ₄₀ EV ₆₀ with was used as sample B-PP ₄₀ EV ₆₀ with.

[Tensile test in Experimental Example 3]
In Experimental Example 3, a tensile test was performed as in Experimental Examples 1 and 2. Table 11 shows the elastic modulus, yield stress, elongation at break, and tensile strength of each sample film obtained from the stress-strain curve.

  By comparing the results of the stress-strain measurement shown in Tables 8 and 11, it becomes clear that when the blend resin contains a compatibilizing agent, the mechanical properties of the sample film such as yield stress, elongation at break and tensile strength are improved. It was.

[Measurement of gas permeation amount in Experimental Example 3]
In Experimental Example 3, the gas permeation amount of oxygen was measured under the same measurement conditions using the same apparatus as in Experimental Examples 1 and 2. As shown in FIG. 8, it was shown that each sample according to Experimental Example 3 had a smaller oxygen gas permeation amount as the mixing ratio of EVOH in the blend resin was higher.

Further, based on the oxygen gas permeation amount data shown in FIG. 8, the oxygen gas permeation coefficient _GP and the _GP reduction rate R with respect to the PP film, which are calculated by the above-described Equations 5 and 6 in the same manner as in Experimental Example 2. _P is shown in Table 12. Incidentally, _G P, value of _{R P} in Table 12 are those obtained by converting a film thickness of 20 [mu] m.

Based on the data shown in Tables 9 and 12, EVOH of each sample according to Experimental Example 2 (each sample not including a compatibilizer) and each sample according to Experimental Example 3 (each sample including a compatibilizer). reduction of the gas permeability coefficient G _P of the mixed ratio and the oxygen was compared the relationship between R _P, was the result shown in FIG. Each sample containing the compatibilizing agent, than the sample containing no compatibilizer, it reduced rate R _P transmission coefficient G _P of the oxygen gas on PP film is small is indicated. Compared with each sample not containing the compatibilizer, each sample containing the compatibilizer has an EVOH mixing ratio of 15 to 50% by weight, particularly when the EVOH mixing ratio is 20 to 50% by weight. Thus, it was shown that a remarkable gas barrier property was exhibited against oxygen gas.

[Experimental Example 4]
[Method for Producing Sample According to Experimental Example 4]
As a resin raw material, EVOH similar to that prepared in Experimental Examples 1 to 3, and PP having a lower viscosity than PP prepared in Experimental Examples 1 to 3 (hereinafter referred to as “HvPP”) (hereinafter referred to as “LvPP”). ) Was prepared. Table 13 shows LvPP characteristic values measured in the same manner as in Experimental Example 1.

In the same manner as that for preparing resin B-PP ₆₀ EV ₄₀ in Experimental Example 2, in Experimental Example 4, blend resin B-LvPP was added at a mixing ratio of LvPP and EVOH of 60:40 without adding a compatibilizer. ₆₀ EV ₄₀ was prepared. Thereafter, a sample B-LvPP ₆₀ EV ₄₀ was produced as a sample film using the resin B-LvPP ₆₀ EV ₄₀ by the same production method as that of the sample according to Experimental Example 2.

[Measurement of gas permeation amount in Experimental Example 4]
In Experimental Example 4, the gas permeation amount of oxygen was measured under the same measurement conditions using the same apparatus as in Experimental Examples 1 to 3. Then, based on the oxygen gas permeation amount of data, according to Equation 5 and 6 described above in the same manner as in Experimental Example 2, was calculated reduction rate R _P of the oxygen gas permeation coefficient G _P for PP film B. Samples _B-LvPP 60 _{EV 40} is the value of _{G P} is smaller than the PP film B, the _{R P} was less than 50%.

[Structural Observation in Experimental Example 4]
In Experimental Example 4, a sample was photographed with an SEM in the same manner as in Experimental Examples 1 and 2. As shown in FIG. 10, in sample B-LvPP ₆₀ EV ₄₀ , it was confirmed that the EVOH dispersed phase formed large spheres in the LvPP matrix.

In Sample B-PP ₆₀ EV _{40 according} to Experimental Example 2 described above, the EVOH dispersed phase formed a layer near the surface in the HvPP matrix, as shown in FIG. 6C. On the other hand, in the sample B-LvPP ₆₀ EV ₄₀ shown in FIG. 10, since the viscosity of the LvPP matrix is low, the dispersed phase can move freely in the LvPP matrix phase, and as a result, the individual dispersed phases have the surface area. It is thought that the smallest spherical phase was formed.

  The molded body according to the present invention is widely applied to the fields of packaging containers for foods and cosmetics, and storage tanks for volatile liquids.

2: Molded body 4: EVOH phase 6: PP matrix phase 10: Layer

Claims (5)

A molded product obtained by molding a blend resin mainly composed of polypropylene (PP) and an ethylene-vinyl alcohol copolymer (EVOH) into a shell shape, a plate shape, a cylindrical shape, or a film shape,
The EVOH is dispersed in the PP to form a dispersed phase, and the dispersed phase forms a layer substantially parallel to the plane direction at least near the surface, and the weight ratio of the PP to the EVOH is 15:85 to 85: 15 is a molded body.   2. The molded body according to claim 1, wherein a melt flow rate (MFR) at a temperature of 200 ° C. and a load of 2.16 kg of the PP is smaller than an MFR at a temperature of 200 ° C. and a load of 2.16 kg of the EVOH.   The molded body according to claim 1 or 2, wherein a weight ratio of the PP to the EVOH is 15:85 to 75:25, and the blend resin contains a compatibilizer of 0.5 to 10 phr. It is a manufacturing method of the forming object according to claim 1 or 2,
A melt blending step of obtaining a blend resin by melting while shearing PP and EVOH as main components;
A molding step of molding the blended resin into a shell, plate, cylinder, or film shape to form a molded product;
Stretching the molded product in one direction parallel to the surface direction of the molded product and in another direction perpendicular to the one direction and parallel to the surface direction,
The manufacturing method of the molded object whose weight ratio of said PP of said blend resin and said EVOH is 15: 85-85: 15. It is a manufacturing method of the forming object according to claim 3,
A melt blending step of obtaining a blend resin by melting while shearing PP and EVOH as main components;
A molding step of molding the blended resin into a shell, plate, cylinder, or film shape to form a molded product;
Stretching the molded product in one direction parallel to the surface direction of the molded product and in another direction perpendicular to the one direction and parallel to the surface direction,
The manufacturing method of the molded object whose weight ratio of said PP of said blend resin and said EVOH is 15: 85-75: 25, and this blend resin contains 0.5-10 phr of compatibilizers.