JP4194888B2 - Composite molded article and manufacturing method thereof - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a composite molded article in which a large number of other resin materials are present in a thin layer in polyolefin, and a method for producing the same. Product and a manufacturing method thereof.
[0002]
[Prior art]
As a container for storing foods, medicines and the like that are highly sensitive to a gas such as oxygen, a container having a high gas barrier property is required together with a lid. Therefore, a gas barrier resin is used for such a container.
However, since a gas barrier resin (for example, nylon or ethylene-vinyl alcohol copolymer) is expensive, a gas barrier container is usually a laminated container in which a gas barrier layer is laminated on an inexpensive structural material. . An example of such a laminated container is a laminated container in which a gas barrier layer made of nylon and a polyolefin as a structural material are laminated. The same applies to gas barrier lids.
[0003]
Such gas barrier containers also have manufacturing problems. That is, as a general container molding method, a molding method including an injection process such as an injection molding method or a stretch blow molding method uses a core to obtain a hollow product, and thus must be a wide-mouthed container. Although there is a problem that it does not exist, it is widely used because it has a high molding speed and as a result inexpensive products can be obtained.
However, molding of a laminated container by a molding method including an injection process is difficult for structural and molding reasons, and there are few examples. For example, a two-color or multilayer injection molding method can be used, but a special apparatus is used. Therefore, it has not been possible to obtain an inexpensive gas barrier container by a molding method including an injection process.
[0004]
In addition, as a composite container made of a plurality of different resin materials, for example, a container in which many blends of polyamide and polyvinyl alcohol are present in a thin layer in polyolefin is disclosed in JP-A-1-275137 (Patent Document 1). ) Is proposed. Such containers are excellent in resistance to liquids such as gasoline and alcohol.
[0005]
By the way, containers for storing foods, pharmaceuticals and the like are used in various environments. In particular, under high humidity, polar polymers (gas barrier resins) are easily affected and their functions (gas barrier properties) are likely to change. Therefore, a practical container is required to maintain gas barrier properties under high humidity in addition to cost.
[0006]
Therefore, the container proposed in Patent Document 1 will be examined. In Example 5 of Patent Document 1, a composite container made of polyethylene alcohol and a blend of amorphous nylon and polyethylene is obtained. Here, amorphous nylon has a gas barrier property, but polyvinyl alcohol used in combination with it is a material whose gas barrier property is lowered under high humidity. For this reason, this container shows a decrease in gas barrier properties when used under high humidity.
In Comparative Example 1 of Patent Document 1, a composite container made of nylon and polyethylene is obtained. However, the nylon used is not amorphous nylon, and therefore, this container shows a decrease in gas barrier properties when used under high humidity.
[0007]
As described above, Patent Document 1 has no recognition of gas barrier properties and, of course, does not disclose or suggest any knowledge of gas barrier properties under high humidity. This is supported by measuring the liquid permeability (ASTM D2684 liquid permeability test) in the example of Patent Document 1. In the diffusion of liquid and gas, gas is much easier to diffuse, and even if the container of Patent Document 1 is excellent in resistance to liquid, it is difficult to predict gas barrier properties from this.
Moreover, Patent Document 1 basically discloses only a container by a blow molding method.
[0008]
As described above, molded products such as containers and lids that are excellent in gas barrier properties even at high humidity of course during drying and can be obtained at low cost by a molding method including an injection process have not been known so far. It was.
[0009]
[Patent Document 1]
JP-A-1-275137
[0010]
[Problems to be solved by the invention]
Therefore, an object of the present invention is to provide a composite molded article that is excellent in gas barrier properties even under high humidity and can be obtained at low cost by a molding method including an injection process.
[0011]
[Means for Solving the Problems]
That is, the composite molded product of the present invention comprises (a) polyolefin 50-99% by mass And (b) amorphous polyamide 1-50% by mass Is a molded product formed through an injection process, and (a) in the polyolefin 0.5-50μm thick Thin layer (b) amorphous polyamide Unevenly distributed near the inner and outer surfaces It is characterized by the presence of a plurality.
[0012]
Here, it is desirable that the thin-layered (b) amorphous polyamide is unevenly distributed near the surface.
The (a) polyolefin is preferably polyethylene.
Moreover, (b) amorphous polyamide is a polymer of diamine and dicarboxylic acid, and it is desirable that either diamine or dicarboxylic acid is an aromatic compound.
Further, it is desirable that the layered structure molded product contains (c) an adhesive resin that exhibits adhesion to both (a) polyolefin and (b) amorphous polyamide.
[0013]
Moreover, it is desirable that the melt viscosity of (b) amorphous polyamide is lower than the melt viscosity of (a) polyolefin.
Such a composite molded article is preferably a container or a lid.
Further, it is desirable that the thin-layered (b) amorphous polyamide is unevenly distributed near the inner surface and the outer surface of the container or the lid.
[0014]
In addition, the present invention (A) A thin layered (b) amorphous polyamide having a thickness of 0.5 to 50 μm is unevenly distributed near the inner surface and the outer surface in the polyolefin. The manufacturing method of the composite molded product is: (a) polyolefin 50-99% by mass and The average particle size of the particles is 1-5 mm (B) Amorphous polyamide 1-50% by mass And a step of forming a heterogeneous molten mixture including the step of molding the heterogeneous molten mixture by a molding method including an injection step.
Here, as (b) amorphous polyamide, it is desirable to use a thing whose melt viscosity at the time of an injection process is lower than the melt viscosity of (a) polyolefin.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
<Composite molded product>
The composite molded article of the present invention is a molded article obtained by molding a mixture containing (a) a polyolefin and (b) an amorphous polyamide through an injection process. (A) A thin-layered (b) amorphous polyamide in the polyolefin There are multiple.
Specifically, as shown in FIG. 1, a number and substantial number of (a) polyolefin 1 is in the form of a continuous matrix phase, and (b) amorphous polyamide 2 is embedded in the continuous matrix phase. Are in the form of a discontinuous dispersed phase which is substantially parallel and spaced apart.
[0016]
As the composite molded article of the present invention, it is preferable that the thin-layered (b) amorphous polyamide 2 is unevenly distributed near at least one surface. As shown in FIG. 2, the thin-layered (b) amorphous polyamide 2 is used. More preferably, 2 is unevenly distributed near both surfaces. Such a composite molded article is very excellent in gas barrier properties.
[0017]
The dimensions of the composite molded product of the present invention are not particularly limited, but in the case of a container, the thickness is 0.5 mm or more, preferably 20 mm or less, and even a large capacity is up to several tens of liters. The lid is not particularly limited to the lid for the container, but a lid for the container is typically exemplified.
[0018]
<(A) Polyolefin>
The (a) polyolefin in the present invention is a homopolymer or copolymer of an olefin such as ethylene, propylene, butene-1,4-methylpentene-1, hexene-1, octene-1.
[0019]
Examples of (a) polyolefin include polyethylene, polypropylene, polybutylene and the like. Among these, polyethylene which is a homopolymer of ethylene or a copolymer of ethylene and an α-olefin is preferable in that it can be high, medium and low density.
[0020]
In addition, as the polyethylene, any of polyethylene produced by a high pressure radical polymerization method, polyethylene produced by a transition metal catalyst such as a chromium catalyst, a Ziegler catalyst, and a metallocene catalyst can be used.
As the (a) polyolefin, an appropriately modified one can be used, but it is necessary to select one that is incompatible with the (b) amorphous polyamide at the time of melting.
[0021]
The type of polyethylene can be selected according to the physical properties required for the molded product such as a container. For example, high-density polyethylene is suitable for molded products that require mechanical strength such as rigidity. (A) When a high-rigidity polyolefin such as high-density polyethylene is used as the polyolefin, a gas barrier container or lid having sufficient mechanical strength can be obtained even if it is thin. In addition, when a soft material such as low-density polyethylene is used as (a) polyolefin, for example, a gas barrier squeeze bottle that can be squeezed out can be obtained.
[0022]
The content of (a) polyolefin in the composite molded article of the present invention is preferably 50 to 99 mass%, most preferably 70 to 96 mass% in the composite molded article. Here, the total of (a) polyolefin and (b) amorphous polyamide is 100% by mass.
[0023]
<(B) Amorphous polyamide>
The (b) amorphous polyamide in the present invention is also referred to as amorphous polyamide or amorphous polyamide, and refers to a polymer different from crystalline or semicrystalline nylon. (B) Amorphous polyamide is defined as a polyamide that does not exhibit a clear melting point when measured by a differential scanning calorimeter (DSC) used in a conventional method. For example, crystalline or semi-crystalline nylon such as nylon 6, nylon 9, nylon 11 and nylon 12 exhibits a predetermined melting point.
[0024]
(B) As an amorphous polyamide, the polymer of diamine and dicarboxylic acid is mentioned, for example.
Examples of the diamine include hexamethylene diamine, 2-methylpentamethylene diamine, 2,2,4-trimethylhexamethylene diamine, bis (4-aminocyclohexyl) methane, 1,4-diaminobutane, and 1,3-diaminopropane. , P-xylenediamine and the like.
Examples of the dicarboxylic acid include isophthalic acid, terephthalic acid, alkyl-substituted iso- or terephthalic acid, adipic acid, and sebacic acid.
[0025]
The above diamine and dicarboxylic acid can be used in appropriate combination as long as the resulting polyamide is amorphous. Usually, in order to obtain an amorphous polyamide, either diamine or dicarboxylic acid may be an aromatic compound and the other may be an aliphatic compound.
(B) Specific examples of the amorphous polyamide include hexamethylene diamine isophthalamide, hexamethylene diamine isophthalamide / terephthalamide copolymer, 2,2,4-hexamethylene diamine and 2,4,4-hexamethylene diamine. Examples thereof include terephthalamide of a mixture.
[0026]
(B) It is preferable that the weight average molecular weight of an amorphous polyamide is 5000 or more.
Examples of commercially available amorphous polyamides include Grivory G21 manufactured by Ems Hemmy and NOVAMID X21 manufactured by Mitsubishi Engineering Plastics.
As the (b) amorphous polyamide, an appropriately modified one can be used, but it is necessary to select one that is incompatible with the (a) polyolefin at the time of melting.
[0027]
The content of (b) amorphous polyamide in the composite molded product of the present invention is preferably 1 to 50% by mass, and most preferably 4 to 30% by mass in the composite molded product. Here, the total of (a) polyolefin and (b) amorphous polyamide is 100% by mass.
[0028]
<(C) Adhesive resin>
When it is desired to improve the interlayer adhesive strength between (a) polyolefin and thin-layered (b) amorphous polyamide in the composite molded article of the present invention, (c) an adhesive resin having adhesiveness is added to both. Can do.
[0029]
(C) As adhesive resin, the polyolefin which has a carbonyl group is mentioned, for example. Examples of the polyolefin having a carbonyl group include a polyolefin having a carboxylic acid moiety bonded to either the main chain or the side chain of the polyolefin. Here, the “carboxylic acid moiety” means carboxylic acid, its ester, acid anhydride, and carboxylate. Carboxylate is a neutralized carboxylic acid. These are sometimes referred to as ionomer polymers.
Polyolefins having carbonyl groups can be prepared by direct synthesis or grafting reactions. An example of direct synthesis is copolymerization of an α-olefin and a monomer having a carboxylic acid moiety. An example of a grafting reaction is graft addition of a monomer having a carboxylic acid moiety to a polyolefin.
[0030]
Examples of the polyolefin used in the graft reaction include polyethylene, a copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms, an α-olefin having 3 to 8 carbon atoms and a non-conjugated diolefin (for example, 1, 4 -A copolymer with hexadiene). As monomers having a carboxylic acid moiety, methacrylic acid, acrylic acid, ethacrylic acid, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethyl maleate, monoethyl maleate, di-maleate n-butyl, maleic anhydride, maleic acid, fumaric acid, itaconic acid, monoesters of these dicarboxylic acids, dodecenyl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, nadic anhydride ( 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride).
The polyolefin having a carbonyl group preferably contains at least 75 mol% of an olefin component and 0.2 to 25 mol% of a carbonyl group.
[0031]
When the carboxylic acid moiety is a carboxylic acid, the carboxylic acid is neutralized with a metal ion having a valence of 1-3, and when the carboxylic acid moiety is a dicarboxylic acid, the dicarboxylic acid has a valence of 1. It is preferable that the metal ion is neutralized. In order to control the degree of neutralization, it is preferable that a sufficient amount of metal ions is present to neutralize at least 10 mol% of the carboxylic acid moiety.
[0032]
(C) Adhesive resin can be made to exist in the quantity of 0.25-30 mass% in a composite molded article, and it is preferable to make it exist in the quantity of 2-20 mass%. Here, the total of (a) polyolefin, (b) amorphous polyamide, and (c) adhesive resin is 100% by mass.
[0033]
<Other ingredients>
In the composite molded article of the present invention, usual additions such as an antioxidant, an ultraviolet absorber, a crosslinking agent, an inorganic filler, a pigment, a foaming agent, a slip agent, and an antistatic agent are within the scope of the present invention. An agent may be added.
However, it is preferable that a resin, an additive, or the like that deteriorates the gas barrier property of the composite molded article under high humidity, such as polyvinyl alcohol, is not blended.
[0034]
<Production method of composite molded product>
The composite molded article of the present invention is a process having a step of preparing a heterogeneous melt mixture containing (a) a polyolefin and (b) an amorphous polyamide, and a step of molding the heterogeneous melt mixture by a molding method including an injection step. It can be obtained by the method.
Specifically, for example, (a) polyolefin particles and (b) amorphous polyamide particles are mixed, the mixture is heated to prepare a heterogeneous melt mixture, and (b) an elongated polyamide made of amorphous polyamide. The heterogeneous molten mixture is preferably molded by a molding method including an injection step so that a discontinuous dispersed phase is formed.
[0035]
Hereinafter, an example of a method for producing a composite molded product will be described in detail.
(I) Preparation of heterogeneous melt mixture:
First, polymer particles ((a) polyolefin particles and (b) amorphous polyamide particles) in a non-molten state are sufficiently dry blended beforehand. The dry blending of the polymer particles can be performed by a known means such as a V-type mixer or a rotary mixer.
[0036]
Next, the mixture obtained by dry blending is heated at a temperature higher than the melting point of the polymer particles having the highest melting point and melted to prepare a heterogeneous molten mixture.
The heating temperature must be such that (b) the amorphous polyamide can be softened or melted at a glass transition temperature or higher and stretched. (B) Since amorphous polyamide does not exhibit a melting point, the “melting point” here refers to the temperature at which the polymer particles are softened to such an extent that they can be stretched in the injection process.
Heating can be performed by various known means. Usually, it can be carried out in an injection molding machine.
[0037]
Care must be taken to substantially avoid further mixing after the polymer particles are heated to melting. Since the heterogeneous molten mixture is homogenized by intense mixing, there is a possibility that a molded article having no discontinuous dispersed phase composed of a thin-layered (b) amorphous polyamide may be obtained. That is, by maintaining the heterogeneity of the molten mixture of (a) polyolefin and (b) amorphous polyamide, when the heterogeneous molten mixture flows in the pipe in the post-injection step, (a) In the continuous matrix phase, (b) the amorphous polyamide can be stretched into a thin layer to become a discontinuous dispersed phase. As long as the molten mixture maintains non-uniformity, these polymer particles may be mixed even if they are in a softened or molten state.
[0038]
The size of the particles of (b) amorphous polyamide in the heterogeneous melt mixture is such that (b) the amorphous polyamide in (b) the continuous matrix phase of the polyolefin as the heterogeneous melt mixture flows through the tube during the injection process. Must be large enough to be stretched into a thin layer into a discontinuous dispersed phase. (B) If the size of the amorphous polyamide particles is too small, even if excessive mixing is not performed, a homogeneous molten mixture is obtained, resulting in a discontinuous dispersion of the thin-layered (b) amorphous polyamide. A phase may not be obtained. (B) If the size of the amorphous polyamide particles is too large, (a) the continuous matrix phase of the polyolefin tends to collapse. (B) The average particle diameter of the amorphous polyamide particles is preferably 1 to 5 mm, more preferably 2 to 4 mm. The average particle diameter of the (b) amorphous polyamide particles is preferably selected so as to obtain a thin-layered (b) amorphous polyamide having a thickness of 0.5 to 50 μm.
[0039]
The heterogeneous melt mixture may be prepared by melting the polymer having the lower melting point in advance and adding the polymer particles having the lower melting point to the melt. Specifically, the heterogeneous molten mixture may be prepared by adding particles of amorphous polyamide (b) in an unmelted state to molten (a) polyolefin and then further heating them.
[0040]
When (c) adhesive resin is used in combination, (a) polyolefin particles, (b) amorphous polyamide particles, and (c) adhesive resin particles can be mixed together.
[0041]
(Ii) Molding of composite molded products:
Molding of the composite molded product is performed by a molding method including an injection step of injecting a heterogeneous mixture. Examples of such a molding method include an injection blow molding method and a stretch blow molding method. That is, the stretch blow molding method is a molding method including an injection process because the parison is once molded by the injection molding method and then taken out from the mold and stretched and further subjected to blow molding. As described above, any method may be used as long as it includes an injection step of once injecting the metal mold.
[0042]
Molding by the injection molding method is performed by injecting a heterogeneous mixture into the mold from various gates, then cooling and solidifying, and then opening the mold and taking out the composite molded product.
Thus, in the method for producing a composite molded article of the present invention, the heterogeneous mixture can be injected and molded at a time in the same manner as in a normal injection molding method. Therefore, since an ordinary injection molding apparatus can be basically used as the apparatus, it is extremely advantageous industrially. The stretch blow molding method described below is the same in that a normal apparatus can be used. On the other hand, the conventional two-color or multilayer injection molding method or the like is a method in which the resin of each layer is injected sequentially or alternately, so that a special device is naturally required.
[0043]
The stretch blow molding method is a method in which a heterogeneous mixture is injected into a mold by an injection molding method to form a parison, then the mold is opened to take out the parison, and this is stretched and blown. More specifically, after injecting the heterogeneous mixture into the mold, the parison is taken out from the mold in a state where it is still stretchable, and the hot parison method of stretching the parison; the heterogeneous mixture is put into the mold Any of the cold parison methods in which the injected and cooled parison is taken out of the mold, reheated so as to be stretched, and stretched can be employed. In either case, a composite molded product can be obtained by sandwiching the parison between two molds and blowing the parison almost simultaneously with blowing the parison.
[0044]
As specific molding conditions in these molding methods, since the continuous matrix phase in the composite molded product of the present invention is polyolefin, the molding conditions in the conventional injection molding method and stretch blow molding method for polyolefin containers and lids are adopted. can do. Basically, if a heterogeneous mixture is molded according to the molding conditions of polyolefin, (a) a composite in which a discontinuous dispersed phase of (b) amorphous polyamide is distributed in a continuous matrix phase made of polyolefin. A molded product is obtained. It is not necessary to adopt the same molding method as the molding method for the container and the lid, which is an example of the composite molded product of the present invention.
[0045]
Here, by adjusting the relative height relationship between the melt viscosity of (a) polyolefin and the melt viscosity of (b) amorphous polyamide during the injection step of the heterogeneous melt mixture, The layered (b) amorphous polyamide is distributed almost evenly in the (a) polyolefin, the thin layered (b) polyamide layer is unevenly distributed in the center of the molded product, or (a ) Polyolefin can be unevenly distributed, that is, the thin-layered (b) amorphous polyamide can be unevenly distributed near the inner surface and the outer surface.
Here, since the melt viscosity of (a) polyolefin and (b) amorphous polyamide is influenced by molding conditions during the injection process, specifically, temperature, shear rate, etc., (a) b) The relative height relationship with the melt viscosity of the amorphous polyamide is the relative height relationship during the injection process.
[0046]
When (a) the polyolefin has a relatively high melt viscosity and (b) the amorphous polyamide has a relatively low melt viscosity, as shown in FIG. 2, (a) the polyolefin is unevenly distributed in the center of the molded product. That is, there is a tendency that the thin-layered (b) amorphous polyamide is unevenly distributed near the inner surface and the outer surface. When the relative height relationship of melt viscosity is reversed, the relative relationship of arrangement tends to be the opposite.
[0047]
In order to make a difference in melt viscosity in this way, (1) materials with originally different melt viscosities may be selected, or (2) melt viscosities for (a) polyolefin and (b) amorphous polyamide, respectively. Alternatively, a method may be employed in which resins having different temperature gradients are selected, and a temperature region in which the melt viscosity is different is selected and molded. In addition, it may be difficult to create a thin layer structure between materials having a very large difference in melt viscosity. Therefore, in practice, it is preferable to appropriately determine the material and molding conditions while molding.
[0048]
In the present invention, since molding is easy and gas barrier properties can be improved, it is preferable that the thin-layered (b) amorphous polyamide is unevenly distributed and localized near the inner surface and the outer surface of the molded product. The uneven distribution, the degree of localization, the range, etc. can be easily determined by appropriately coloring either or both of (b) amorphous polyamide and (a) polyolefin, and then appropriately cutting the molded product after molding. . By appropriately confirming the difference in melt viscosity between the two materials while judging in this way, it is easy to obtain a composite molded product in which the thin-layered (b) amorphous polyamide is unevenly distributed near the inner surface and the outer surface. be able to.
[0049]
After molding, the molded product is solidified by cooling the molded product to a temperature lower than the melting point of the material having the lowest melting point. Cooling can be performed by any desired means and at an appropriate rate. In the case of the injection molding method, the molded product is often cooled by cooling the mold.
[0050]
In the composite molded product of the present invention described above, since a mixture containing (a) polyolefin and (b) amorphous polyamide is molded through an injection process, a special injection molding apparatus should be used. And can be manufactured inexpensively. In addition, since (a) a plurality of thin-layered (b) amorphous polyamides are present in the polyolefin, it is possible to reduce the number of inexpensive (a) polyolefins and expensive (B) amorphous polyamides. Cost can also be reduced. Thus, conventionally, multilayer molded articles to which gas barrier properties have been imparted have been expensive, but the composite molded article of the present invention can be obtained by a molding method including an injection process, and an inexpensive polyolefin can be obtained. Combined with the main molded product, it becomes an inexpensive product as a final product.
[0051]
In addition, since (a) a plurality of thin-layered (b) amorphous polyamides are present in the polyolefin, the gas permeability of oxygen and the like is low and a good gas barrier compared to a single layer of polyolefin. Showing gender. Further, since the material imparting gas barrier properties is (b) amorphous polyamide, the gas barrier properties are excellent even under high humidity.
[0052]
Moreover, in the manufacturing method of the composite molded article of this invention demonstrated above, the process of preparing the heterogeneous melt mixture containing (a) polyolefin and (b) amorphous polyamide, and the injection | pouring process of a heterogeneous melt mixture are carried out. Use a special injection molding apparatus even if it is an injection molding method that has conventionally been difficult to obtain a hollow multilayer molded product having a gas barrier layer. Therefore, it is possible to easily and inexpensively obtain a composite molded product having excellent gas barrier properties, such as a container and a lid.
The present inventors have found for the first time that an inexpensive composite molded article excellent in gas barrier properties, such as a container and a lid, can be obtained by a molding method represented by such an injection molding method, including an injection process. is there.
[0053]
The composite molded article of the present invention is suitable for a container that contains contents sensitive to oxygen or the like, for example, foods, medicines, and the like, and its lid. In particular, it is suitable for containers and lids used under high humidity because gas barrier properties are maintained at a high level and not deteriorated not only during drying but also under high humidity. The composite molded article of the present invention has low gas permeability such as oxygen and gas barrier properties as compared with a single layer of polyolefin.
A particularly preferable composite molded article is one in which the thin-layered (b) amorphous polyamide is unevenly distributed and localized near the inner surface and the outer surface, and the composite molded article having such a structure has a high gas barrier property.
Examples of the composite molded article of the present invention include a lid as well as a container. Therefore, if both the container and the lid are the composite molded product of the present invention, the gas barrier property will be more satisfactory.
[0054]
【Example】
Hereinafter, the present invention will be described in detail by way of examples.
The following materials were used.
((A) polyolefin)
High density polyethylene (HDPE): MFR 1.0 g / 10 min, density 0.961 g / cm ^Three .
((B) amorphous polyamide)
Grivory G21 (trade name) manufactured by EMS Hemmy.
((C) Adhesive resin)
Maleated polyethylene: maleic anhydride content 0.29% by mass, MFR 0.5 g / 10 min.
[0055]
90% by mass of HDPE, 5% by mass of Grivoli G21 and 5% by mass of maleated polyethylene were mixed in advance. This mixture is supplied to an injection molding machine (manufactured by Toshiba), heated and melted to form a heterogeneous molten mixture, which is then injection-molded under the following molding conditions, and a round bottle (with a wall thickness of about 1.0 mm and a volume of 300 ml) Container).
(Molding conditions) Barrel temperature: 230 ° C., nozzle temperature: 230 ° C., mold temperature: 20 ° C., injection time: 2.5 seconds, cooling time: 5.5 seconds, cycle time 10 seconds.
[0056]
When the surface and cut surface of the obtained bottle were visually observed, the Grivoli G21 covered the inner and outer surfaces of the bottle with almost no gap and was unevenly distributed near the inner and outer surfaces. On the other hand, it was confirmed that only the HDPE was present, with almost no Grivoli G21 being observed in the center of the bottle. This structure was easily visible by blending and molding a small amount of coloring components in either or both of Grivoli G21 and HDPE.
[0057]
Moreover, about the obtained bottle, the oxygen permeation amount was measured by the following method. As a result, the oxygen permeation amount was reduced by 50% compared to the bottle of HDPE monolayer having the same thickness. This shows that the oxygen permeation amount does not change even after the bottle is left in an environment of room temperature 25 ° C. and humidity 75% RH for 30 days, and is excellent in moisture resistance.
[0058]
(Measurement method of oxygen transmission rate)
In the glow box substituted with nitrogen, the mouth of the test bottle was sealed with aluminum foil to prevent leakage from the mouth. The oxygen concentration in the glow box was measured and used as the initial value. The sealed bottle was stored in a room with a room temperature of 25 ° C. and a humidity of 75% RH for 30 days. Since oxygen permeates from the bottle wall during indoor storage, the oxygen concentration in the bottle was determined by measuring the oxygen concentration inside the bottle.
[0059]
【The invention's effect】
As explained above, the composite molded article of the present invention is composed of (a) polyolefin. 50-99% by mass and The average particle size of the particles is 1-5 mm (B) Amorphous polyamide 1-50% by mass Is a molded product formed through an injection process, and (a) in the polyolefin 0.5-50μm thick Thin layer (b) amorphous polyamide Unevenly distributed near the inner and outer surfaces Since there are a plurality of them, they are excellent in gas barrier properties even at high humidity and are inexpensive.
[0060]
Moreover, the manufacturing method of the composite molded product of this invention shape | molds the process which prepares the heterogeneous melt mixture containing (a) polyolefin and (b) amorphous polyamide, and the molding method including an injection process. Therefore, it is possible to easily obtain a composite molded article that is excellent in gas barrier properties and is inexpensive even under high humidity.
[Brief description of the drawings]
FIG. 1 is a schematic sectional view showing an example of a composite molded article of the present invention.
FIG. 2 is a schematic sectional view showing another example of the composite molded article of the present invention.
[Explanation of symbols]
1 (a) Polyolefin
2 (b) Amorphous polyamide

Claims (10)

(A) A mixture containing 50 to 99% by mass of polyolefin and (b) 1 to 50% by mass of amorphous polyamide is a molded product formed through an injection process,
(A) A composite molded article characterized in that a plurality of thin (b) amorphous polyamides having a thickness of 0.5 to 50 μm are unevenly distributed in the vicinity of the inner surface and the outer surface in the polyolefin.   The composite molded article according to claim 1, wherein the thin-layered (b) amorphous polyamide is unevenly distributed near the surface.   (A) Polyolefin is polyethylene, The composite molded article of Claim 1 or Claim 2 characterized by the above-mentioned.   (B) Amorphous polyamide is a polymer of diamine and dicarboxylic acid, and either diamine or dicarboxylic acid is an aromatic compound. Composite molded product.   5. The layered structure molded article contains (c) an adhesive resin that exhibits adhesion to both (a) polyolefin and (b) amorphous polyamide. A composite molded article as described in 1.   The composite molded article according to any one of claims 1 to 5, wherein the melt viscosity of the amorphous polyamide (b) is lower than the melt viscosity of the polyolefin (a).   The composite molded article according to claim 1, wherein the composite molded article is a container or a lid.   8. The composite molded article according to claim 7, wherein the thin-layered (b) amorphous polyamide is unevenly distributed near the inner surface and the outer surface of the container or lid. (A) preparing a heterogeneous melt mixture containing 50 to 99% by weight of polyolefin and 1 to 50% by weight of amorphous polyamide (b) having an average particle diameter of 1 to 5 mm ;
And (a) a thin layer of 0.5 to 50 μm thick (b) amorphous polyamide in the vicinity of the inner surface , characterized in that it comprises a step of molding a heterogeneous molten mixture by a molding method including an injection step And the manufacturing method of the composite molded product which is unevenly distributed near the outer surface and exists in plurality .   The method for producing a composite molded article according to claim 9, wherein (b) amorphous polyamide is used whose melt viscosity during the injection process is lower than that of (a) polyolefin.

Images