JP2019123531A - Laminate tube container and its manufacturing method - Google Patents

Abstract

To provide a laminate tube container and its manufacturing method which uses polyamide including a meta-xylilene group and polyolefin and of which the mouth and shoulder have high oxygen barrier properties.SOLUTION: Resin composition including polyolefin and polyamide including a meta-xylilene group is heated and mixed, and provided on the opening end on one side of the body part of the laminate tube container and is shrunk to form the shoulder and the mouth. At this time, due to that the heating temperature inside the cylinder is made below the temperature at which polyamide including a meta-xylilene group begins to fuse, the polyamide A1 including a meta-xylilene group phase-separates and spreads in a plane in the direction that obstructs oxygen permeation from outside of the laminate tube container toward inside, and consequently high oxygen barrier properties are exhibited.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a laminate tube, and more particularly to a technique suitable for use in a laminate tube excellent in various barrier properties.

  The laminate tube container has a resin shoulder and an opening attached to one open end of a cylindrically rounded body.

  As a laminate tube container for protecting food, medicines and the like, there is known one using an oxygen barrier material in its body in order to prevent the contents from being oxidized and deteriorated by oxygen in the open air. For example, a plastic film coated with a substance having an oxygen barrier performance is known. Furthermore, there is also known an oxygen barrier material in which aluminum, silica, alumina or the like is vapor-deposited on a film in order to exhibit high oxygen barrier properties.

  Thus, although an oxygen barrier material can be used for the trunk | drum of a lamination tube container, it was difficult to provide barrier property to an opening and a shoulder. Therefore, Patent Document 1 uses a resin composition containing three components of a polyolefin, a modified polyolefin, and a metaxylylene group-containing polyamide as a resin composition that constitutes the mouth and the shoulder, and compression molding the resin composition. A laminated tube container is proposed in which the top and the shoulder are formed. According to this technique, the metaxylylene group-containing polyamide phase separates from the polyolefin and the modified polyolefin to form a sphere, and further, the spherical metaxylylene group-containing polyamide is compressed to be flattened. Since the metaxylylene group-containing polyamide is a resin excellent in oxygen barrier performance, the metaxylylene group-containing polyamide thus deformed into a flat shape interferes with the permeation of oxygen, so that the barrier property of the mouth and shoulders is increased.

JP, 2017-159927, A

  As described above, the metaxylylene group-containing polyamide phase separates from the other resins in the mouth and shoulders of the laminate tube container described in Patent Document 1 to form a flat shape, and the flat metaxylylene group-containing polyamide is dispersed It is in a state of being However, when the flat metaxylylene group-containing polyamide is dispersed in this manner, there are many gaps between the metaxylylene group-containing polyamide and the metaxylylene group-containing polyamide, and the gaps are composed of a polyolefin having poor oxygen barrier properties and a modified polyolefin. Because of this, oxygen gas flows in through this gap. For this reason, in the laminated tube container of patent document 1, high oxygen barrier property was not able to be implement | achieved.

  The present invention has been made based on the above circumstances, and uses a metaxylylene group-containing polyamide and a polyolefin, and further, a laminated tube container having high oxygen barrier properties between the mouth and the shoulder, and a method for producing the same. Intended to be provided.

That is, the invention according to claim 1 is a laminate tube container in which a shoulder and an opening are formed at one open end of a cylindrically formed trunk, wherein the shoulder and the opening are formed. In a laminated tube container comprising a resin composition comprising a polyolefin and a metaxylylene group-containing polyamide,
The laminated tube container is characterized in that the polyamide is phase separated into a surface shape which spreads in a direction that hinders oxygen permeation from the outside to the inside of the laminated tube container.

  Next, the invention according to claim 2 is the laminated tube container according to claim 1, wherein the resin composition contains a modified polyolefin in addition to the polyolefin and the metaxylylene group-containing polyamide.

  Next, the invention according to claim 3 is the laminated tube container according to claim 1 or 2, wherein the melt flow rate (MFR) of the polyolefin is 3 to 7 g / 10 min.

Next, the invention according to claim 4 is a method of manufacturing a laminate tube container by forming a shoulder and an opening on one open end of a cylindrically formed trunk by a compression molding method. In the method of manufacturing a laminated tube container, the shoulder portion and the mouth portion are made of a resin composition containing a polyolefin and a metaxylylene group-containing polyamide,
The resin composition is kneaded with a screw in a cylinder while being heated, and supplied to one open end of the body through an adapter, and the resin composition thus supplied to the open end is compressed to form a shoulder. And forming the head and the mouth,
The method for producing a laminated tube container is characterized in that the heating temperature in the cylinder is made equal to or lower than the melting start temperature of the metaxylylene group-containing polyamide.

  Next, invention of Claim 5 is a melt flow rate (MFR) of the said polyolefin is 3-7 g / 10min, It is a manufacturing method of the lamination tube container of Claim 4 characterized by the above-mentioned.

  In the laminated tube container of the present invention, the shoulder and the mouth are made of a resin composition containing a polyolefin and a metaxylylene group-containing polyamide having a high oxygen barrier property, and the polyamide is phase-separated, Since the planar polyamide and the planar polyamide block oxygen permeation, the laminated tube container has a high oxygen barrier property, since the laminated tube container has a planar shape spreading in the direction that obstructs the oxygen permeation from the outside to the inside of the laminated tube container.

  This laminated tube container can be manufactured by the method according to claim 4 or 5. That is, a resin composition containing a polyolefin and a metaxylylene group-containing polyamide is introduced into a cylinder, and is kneaded with a screw while heating to a temperature equal to or lower than the melting initiation temperature of the tachysilylene group-containing polyamide. By feeding to the open end of the, and compressing and molding, it is possible to form the phase-separated polyamide in the form of an expanded surface in the direction that impedes oxygen permeation.

  When the heating temperature in the cylinder is equal to or higher than the melting point of the polyamide, the phase-separated polyamide becomes spherical, and even if it is compressed, it becomes only a flat shape and high oxygen barrier property is obtained. It is not possible.

  In addition, even if the heating temperature in the cylinder is below the melting point of the polyamide, when the temperature exceeds the melting start temperature, the phase-separated polyamide is a mixture of spherical polyamide and surface-spread polyamide. In this state, although the oxygen barrier property is improved as compared with the case where the temperature is raised to the temperature higher than the melting point, the oxygen barrier property can not be sufficiently high.

  When the melt flow rate (MFR) of the polyolefin is out of the range of 3 to 7 g / 10 min, most of the phase-separated polyamide is spread in a planar state, but the spherical polyamide is also mixed. . For this reason, it is preferable to make the melt flow rate (MFR) of polyolefin into the range of 3-7 g / 10min.

FIG. 1 is a perspective view showing a specific example of a laminated tube container according to the present invention. FIG. 2 is a schematic cross-sectional view showing the manufacturing process in the specific example of the laminate tube according to the present invention. FIG. 3 is a schematic cross-sectional view showing the cross section of the mouth of the laminate tube, and FIG. 3 (a) shows the cross section of the mouth of the specific example of the laminate tube according to the present invention. These show the cross section of the opening part of the example of the lamination tube which concerns on a prior art example.

  Hereinafter, specific examples of the laminated tube according to the present invention will be described based on the drawings.

  FIG. 1 is a perspective view showing a laminated tube, and in the figure, reference numeral 10 is a laminated tube.

  As shown in FIG. 1, the laminate tube 10 has the shoulder 12 and the opening 13 formed by compression molding on one open end (upper open end in the figure) of the heat-resistant cylindrical body 11. At the same time, it is attached by heat welding, and a screw thread 14 for mounting a cap 15 which is a separate body is provided on the outer peripheral surface of the opening 13. The shoulder 12 and the mouth 13 are molded using a single-layer resin as described later.

  The cap 15 may not be provided, and the upper end of the opening 13 may be sealed by a thin body having a barrier property such as aluminum foil. As an example of this seal, a sealing material having a structure in which a biaxially stretched polyethylene terephthalate film, an aluminum foil, and a sealant layer of a polypropylene resin are sequentially laminated from the outside can be thermally bonded to enhance sealing performance.

  Further, the bottom portion 16 of the laminate tube 10 is an unsealed opening before filling of the contents, and is sealed by heat bonding after filling of the contents, for use as a filling port of the contents.

  When the cap 15 is provided, it can be manufactured by injection molding using the same resin as the shoulder 12 and the opening 13. A screw provided on the outer peripheral surface of the opening 13 is provided on the inner peripheral surface of the side wall. A threaded groove 17 may be provided for threadedly engaging the crest 14.

  The body portion 11 is in the form of a tube made of a laminate having a barrier property, and has, for example, an aluminum layer, and the inner surface thereof is made of resin contained in the shoulder portion 12 and the mouth portion 13 and made of polyolefin. ing. The laminate having the barrier property of the body portion 11 is a layer made of aluminum as a barrier layer, a PET layer, an inorganic vapor deposition barrier layer (alumina, silicon oxide etc.) or a metal thin film on a film (PET, nylon etc.) It is possible to have a vapor deposited film, in which the layer is vapor deposited.

  The inner surface of the body portion 11 is preferably made of polyethylene resin in consideration of adhesion with the shoulder portion 12.

The shoulder 12 and the mouth 13 can be formed using a resin composition containing a polyolefin and the polyamide as a material. In addition to the above-mentioned polyolefin and the above-mentioned polyamide, a resin composition containing a modified polyolefin can be used as the material of the shoulder 12 and the mouth 13. In addition, thermoplastic elastomers, various copolymerized polyolefins such as EEA (ethylene-ethyl acrylate), EMA (ethylene-methyl acrylate), ionomers, etc. may be blended for the purpose of modification, and shoulder 13 and A burr generated in the manufacturing process of the mouth portion 12 and a material obtained by crushing a defective product which did not become a product may be mixed.

  Next, each of these materials will be described, and then, a method of manufacturing the laminated tube container of the present invention using each of these materials will be described.

(Meta-xylene group-containing polyamide)
The metaxylylene group-containing polyamide has a diamine unit and a dicarboxylic acid unit, and by including it in the resin composition, can impart an effect of enhancing the oxygen barrier performance of the formed laminated tube.

  The diamine unit constituting the metaxylylene group-containing polyamide is not particularly limited. Specifically, for example, metaxylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bisbis (Aminomethyl) cyclohexane, tetramethylenediamine, hexamethylenediamine, nonanemethylenediamine, 2-methyl-1,5-pentanediamine or the like can be used.

  In addition, as a metaxylene group containing polyimide, what contains 70 mol% or more of metaxylylene diamine units, for example is preferable, what is contained 80 mol% or more is more preferable, and what is contained 90 mol% or more is more preferable. By using a meta-xylene group-containing polyimide containing 70 mol% or more of meta-xylene diamine units as the resin composition, the gas barrier properties in the formed shoulder 13 and the opening 12 and the junction between them and the body 11 can be efficiently made It can be enhanced.

  The dicarboxylic acid unit constituting the metaxylene group-containing polyimide is not particularly limited. Specifically, for example, α, ω-aliphatic dicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid And alicyclic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, xylylene dicarboxylic acid, and naphthalene dicarboxylic acid. Among these, isophthalic acid and 2,6-naphthalenedicarboxylic acid are preferable because they can easily obtain a polyamide having excellent barrier properties without inhibiting the polycondensation reaction when producing a metaxylylene group-containing polyamide. .

  In addition, as the metaxylene group-containing polyimide, for example, those containing 50 mol% or more of dicarboxylic acid units such as α, ω-aliphatic dicarboxylic acids are preferable, those containing 60 mol% or more are more preferable, and those containing 70 mol% or more Is more preferred. By setting the dicarboxylic acid unit to 70 mol% or more, it is possible to prevent the crystallinity of the metaxylene group-containing polyimide from being excessively reduced.

  Specific examples of the α, ω-aliphatic dicarboxylic acid include suberic acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid and the like. Among these, it is preferable to use adipic acid or sebacic acid because it is excellent in performance to maintain good gas barrier properties and crystallinity.

A metaxylene group-containing polyimide is a copolymer unit other than a diamine unit and a dicarboxylic acid unit within the range not impairing the effects of the present invention, such as lactams such as ε-caprolactam and laurolactam, aminocaproic acid, aminoundecanoic acid and the like Aliphatic aminocarboxylic acids,
It may contain an aromatic aminocarboxylic acid such as para-aminomethylbenzoic acid and the like.

  The metaxylylene group-containing polyamide can be produced using a melt polycondensation (melt polymerization) method. Specifically, there may be mentioned, for example, a method in which a nylon salt composed of a diamine and a dicarboxylic acid is heated in the presence of water and under pressure, and polymerized in a molten state while removing the added water and condensation water.

  Moreover, it can also manufacture by the method of polycondensation by adding a diamine directly to the molten dicarboxylic acid. In this case, it is preferable to keep the reaction system in a uniform liquid state. Specifically, it is preferable to carry out the polycondensation reaction while raising the temperature of the reaction system so that the reaction temperature does not fall below the melting point of the oligoamide and polyamide formed while continuously adding the diamine to the dicarboxylic acid.

  A phosphorus atom-containing compound may be contained in the polycondensation system of the metaxylene group-containing polyimide. When the phosphorus atom-containing compound is contained in the polycondensation system of the metaxylene group-containing polyimide, the effect of promoting the amidation reaction and the effect of preventing the coloring during the polycondensation can be obtained.

  The phosphorus atom-containing compound is not particularly limited. Specifically, for example, dimethylphosphinic acid, phenylmethylphosphinic acid, hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, hypophosphorous acid Lithium, ethyl hypophosphite, phenylphosphonous acid, sodium phenylphosphonous acid, potassium phenylphosphonous acid, lithium phenylphosphonous acid, ethyl phenylphosphonous acid, phenylphosphonic acid, ethylphosphonic acid, sodium phenylphosphonate, Potassium phenyl phosphonate, lithium phenyl phosphonate, diethyl phenyl phosphonate, sodium ethyl phosphonate, potassium ethyl phosphonate, phosphorous acid, sodium hydrogen phosphite, sodium phosphite, triethyl phosphite, triphenyl phosphite , Pyrophosphorus Or the like can be used. Among these, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite metal salt and the like are highly effective in promoting the amidation reaction and are also excellent in the color preventing effect. Preferably, sodium hypophosphite is particularly preferred.

  The addition amount of the phosphorus atom-containing compound to be added to the metaxylene group-containing polyimide is preferably 1 to 500 ppm, more preferably 5 to 450 ppm, in terms of phosphorus atom concentration in the metaxylylene group-containing polyamide. More preferably, it is 400 ppm. By setting the addition amount of the phosphorus atom compound in the above-mentioned range, it is possible to prevent the coloring of the xylylene group-containing polyamide during the polycondensation.

  It is preferable that an alkali metal compound or an alkaline earth metal compound is contained together with the phosphorus atom-containing compound in the polycondensation system of the metaxylene group-containing polyimide. By coexistence of an alkali metal compound or an alkaline earth metal compound with a phosphorus atom-containing compound, the amidization reaction rate can be adjusted.

  The alkali metal compound and the alkaline earth metal compound are not particularly limited, but specifically, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, water Alkali metal and alkaline earth metal hydroxides such as calcium oxide and barium hydroxide, and alkali metals and alkalis such as lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, magnesium acetate, calcium acetate, barium acetate and the like And acetates of earth metals and the like.

When an alkali metal compound or an alkaline earth metal compound is added to the metaxylene group-containing polyimide, a value obtained by dividing the number of moles of the alkali metal compound or the alkaline earth metal compound by the number of moles of the phosphorus atom containing compound is 0.5 to 0.5. The range is preferably 2.0, more preferably 0.6 to 1.8, and still more preferably 0.7 to 1.5. By setting the addition amount of the alkali metal compound or the alkaline earth metal compound in the above-described range, it is possible to suppress the formation of gel while obtaining the amidification reaction promoting effect by the phosphorus atom-containing compound.

  The metaxylylene group-containing polyamide obtained by melt polycondensation is once taken out, pelletized, dried and used. Furthermore, solid phase polymerization may be performed to further increase the degree of polymerization. The heating apparatus used for drying or solid phase polymerization is not particularly limited, and known methods and apparatuses can be used. As such a heating device, specifically, for example, a heating device of a continuous type, a tumble dryer, a conical dryer, a rotary dryer or the like called a rotary drum type heating device and a Nauta mixer The conical-type heating apparatus etc. which were equipped with the rotary blade etc. are mentioned. Among these, a batch type heating device can seal the inside of the system and is easy to proceed with polycondensation in a state where oxygen causing the coloring is removed, and is particularly useful when performing solid phase polymerization of polyamide.

  In the metaxylylene group-containing polyamide, an antioxidant, a matting agent, a heat resistant stabilizer, a weather resistant stabilizer, an ultraviolet light absorber, a nucleating agent, a plasticizer, a flame retardant, and an electrification within the range not impairing the effects of the present embodiment. An additive such as an inhibitor, a color inhibitor, a lubricant, an antigelling agent, a clay such as layered silicate, a nanofiller, and the like may be contained. In addition, for the purpose of modifying xylylene group-containing polyamide, various polyamides such as nylon 6 and nylon 66 and non-crystalline nylon using aromatic dicarboxylic acid as a monomer as needed, modified resins thereof, polyolefins and modified resins thereof, You may add the elastomer etc. which have styrene in frame | skeleton.

(Polyolefin)
As the polyolefin, a polyolefin having a melt flow rate (MFR) in the range of 3 to 7 g / 10 min can be preferably used. Specifically, for example, linear low density polyethylene resin, low density polyethylene resin, medium density polyethylene resin, high density polyethylene resin, ultra high molecular weight high density polyethylene resin, polypropylene resin, or selected from ethylene, propylene, butene, etc. Resins comprising copolymers of two or more olefins, and mixtures thereof can be used.

(Modified polyolefin)
The modified polyolefin used in the production method of the present embodiment is obtained by graft-modifying the above-described polyolefin with an unsaturated carboxylic acid or an anhydride thereof. This modified polyolefin is generally used widely as an adhesive resin.

  Specific examples of unsaturated carboxylic acids or anhydrides thereof include acrylic acid, methacrylic acid, α-ethyl acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid and chloromaleic acid. , Butenylsuccinic acid and the like, and acid anhydrides thereof. Among these, it is preferable to use maleic acid and maleic anhydride.

  The method of graft copolymerizing the above-mentioned unsaturated carboxylic acid or its anhydride with polyolefin to obtain a modified polyolefin is not particularly limited, and various conventionally known methods can be used. Specifically, for example, a method of melting a polyolefin using an extruder or the like, adding a graft monomer and copolymerizing it, a method of dissolving a polyolefin in a solvent and adding a graft monomer and copolymerizing it, and the like After making it into a water suspension, the method etc. which add a grafting monomer and copolymerize are mentioned.

(Resin composition)
The content of the metaxylylene group-containing polyamide in the resin composition constituting the shoulder portion 12 and the mouth portion 13 is 100% by mass in total of the polyolefin, the metakirycylene group-containing polyamide, and the modified polyolefin (that is, 100% by mass of the resin composition) On the other hand, it is preferable to set it as 2 to 35 mass%. By setting the metaxylylene group-containing polyamide in the resin composition to the above range, the barrier performance of the shoulder 13 and the mouth 12 can be efficiently enhanced, and the strength reduction of the shoulder 13 and the mouth 12 can be practically used. The adhesion between the shoulder 13 and the body 11 and the barrier performance can be reliably maintained.

  In addition, the content of the polyolefin in the resin composition is 60 to 90 mass% with respect to 100 mass% in total of the polyolefin, the metachrysylene group-containing polyamide, and the modified polyolefin (that is, 100 mass% of the resin composition). Is preferred. By setting the content of the polyolefin in the resin composition to the above range, strength reduction of the container blended with the metaxylylene group-containing polyamide can be minimized.

  In addition, the content of the modified polyolefin in the resin composition is 5 to 30% by mass with respect to 100% by mass in total of the polyolefin, the metachrysylene group-containing polyamide, and the modified polyolefin (that is, 100% by mass of the resin composition). Is preferred. By setting the modified polyolefin in the resin composition in the above-mentioned range, the adhesion between the non-adhesive polyolefin and the metaxylylene group-containing polyamide is improved, and the strength of the shoulder 13 and the mouth 12 is enhanced. The adhesion and barrier performance between the and the body 11 can be reliably maintained.

  In addition, the content of the modified polyolefin relative to the metaxylylene group-containing polyamide in the resin composition is preferably 0.8 to 5.0 times by mass ratio, and more preferably 1.0 to 4.5 times It is more preferable to make it 1.0 to 4.0 times. By setting the content of the modified polyolefin in the above range, the strength of the shoulder 13 and the mouth 12 can be enhanced, and the adhesion between the shoulder 13 and the trunk 11 and the barrier performance can be reliably maintained.

(Method of manufacturing laminated tube container)
Next, the laminated tube 10 can be manufactured by a compression molding method. 2 (a) to 2 (c) show schematic cross-sectional views in the manufacturing process by the compression molding method.

  That is, first, a cylinder-shaped barrier laminate having front and back surfaces made of the same polyolefin as the shoulder 12 and the mouth 13 is prepared as the body 11 and the opening at one end is extended as a connection area Is set in a state of being wound around a cylindrical mold 2B formed in a convex shape (see FIG. 2 (b)).

  Next, as shown in FIG. 2A, the resin composition A is supplied to the extruder. The extruder is composed of three parts, a supply unit, a compression unit, and a measurement unit, and an adapter 23 is connected to the tip thereof.

  The supply unit, the compression unit and the measurement unit of the extruder include a cylinder 21 and a screw 22 disposed inside the cylinder 21. The cylinder 21 is provided with a heating device (not shown).

The supply part is provided with a supply port 21a, and the resin composition A is supplied by charging the respective materials from the supply port 21a. Then, the resin composition A is heated in the compression section, and is kneaded and compressed by the rotation of the screw 22. In addition, as the screw 22 rotates, it is transferred to the measuring unit (in the Z direction in the figure).

  In addition, it is important that the heating temperature is below the melting start temperature of metaxylylene group containing polyamide. When the heating temperature is equal to or higher than the melting point, the metaxylylene group-containing polyamide melts, so that the phase-separated polyamide becomes spherical, and as described later, it becomes only a flat shape even if it is compressed. , High oxygen barrier properties can not be obtained.

  In addition, even if the heating temperature is below the melting point, if the temperature exceeds the melting start temperature, the phase-separated polyamide becomes a state in which the spherical polyamide and the planarly spread polyamide are mixed, and the melting point Although the oxygen barrier property is improved as compared with the case of heating to the above temperature, it can not exhibit a sufficiently high oxygen barrier property.

  On the other hand, when the heating temperature is a temperature equal to or lower than the melting start temperature of the metaxylylene group-containing polyamide, the phase-separated polyamide is spread in a plane extending in the flow direction of the resin composition A and intersects this Block oxygen transmission in the direction. In FIG. 2A, the flow direction of the resin composition A in the cylinder 21 is the Z direction in the drawing, and the flow direction of the resin composition A in the adapter 23 is the A2 direction in the drawing.

  And a measurement part is a part which controls the discharge amount of the resin composition A by the front-end | tip position of the screw 22. As shown in FIG. That is, the discharge amount of the resin composition A can be decreased by bringing the tip end position of the screw 22 close to the adapter 23, and the discharge amount can be increased by keeping the tip of the screw 22 away from the adapter 23.

  Next, the resin composition A discharged from the cylinder 21 is formed of a mold 2B and a mold 2A1C covering the periphery of the mold 2B and having a female shape of a shoulder 13 via an adapter 23. It injects | throws-in to the position used as shaping | molding space (refer FIG.2 (b)).

  Next, as shown in FIG. 2C, after the mold 2A1B is closed at a low pressure (for example, about 784 kPa) and the resin composition is heated (the mold temperature: about 80.degree. C.) to degas, The mold 2A1B is closed under high pressure (mold clamping pressure: about 1960 kPa), and heat and heat of the mold cause the resin to flow and solidify, and the laminate tube container 10 in which the shoulder 13 and the opening 12 and the body 11 are integrated. Manufacture.

(Laminated tube container)
As shown in FIG. 3A, the mouth 13 of the laminate tube container manufactured in this manner is such that the metaxylylene group-containing polyamide A1 is phase-separated from the other resin (for example, polyolefin or modified polyolefin) A2, It shows a planarly spread shape. This surface is accompanied by some waviness, but is along the flow direction of the resin composition A, and therefore, it spreads in the direction that obstructs oxygen permeation from the outside to the inside of the laminated tube container 10. This surface generally has a shape continuously connected from the tip of the mouth to the body, and the length of the short side is usually 50 times or more the thickness. Similarly, also in the shoulder portion 12, the metaxylylene group-containing polyamide A1 phase-separates to form a surface that spreads in a direction that impedes oxygen permeation from the outside to the inside of the laminated tube container.

In addition, while using polyolefin of MFR5g / 10min as a polyolefin and using metaquirycylene group containing polyamide of 230-240 degreeC of melting | fusing point and 210 degreeC of melting | fusing start temperatures as metachrycylylene group containing polyamide A1, the heating temperature in the cylinder 21 is used When the laminated tube container 10 is manufactured as the melting start temperature of the contained polyamide or less, in the shoulder portion 12 and the mouth portion 13, as shown in FIG. Separately, shoulder 12 and mouth 1
It became a plane that extended to the entire range of 3. The oxygen permeability at this time was 0.0009 to 0.0014 cc / pkg · day.

  On the other hand, even when using the same polyolefin and the metakirycylene group-containing polyamide A1, when the heating temperature in the cylinder 21 is set to the melting point of the metakirycylene group-containing polyamide or more, as shown in FIG. The polyamide A1 was only dispersed as flat dots, and the oxygen permeability of the shoulder 12 and the mouth 13 was 0.0137 cc / pkg · day.

  In addition, when the same polyolefin and the metachrysylene group-containing polyamide A1 are used, and the heating temperature in the cylinder 21 is equal to or lower than the melting point and equal to or higher than the melting start temperature, as shown in FIG. A1 shows a state in which a spherical polyamide and a planarly spread polyamide are mixed, and the oxygen permeability of the shoulder 12 and the mouth 13 is 0.0066 cc / pkg · day.

  From this result, by setting the heating temperature in the cylinder 21 to a temperature equal to or lower than the melting start temperature of the metaklysylylene group-containing polyamide, the phase-separated metakrycylylene group-containing polyamide spreads in a planar manner, and as a result, it exhibits extremely high oxygen barrier properties. Can understand.

  When a polyolefin having MFR of 10 g / 10 min is used instead of a MFR of 5 g / 10 min, the same metaquirycylene group-containing polyamide (melting point: 230 to 240 ° C., melting start temperature: 210 ° C.) A1 is used and inside cylinder 21 In the shoulder portion 12 and the mouth portion 13, the phase-separated polyamide A1 is a mixture of spherical polyamide and surface-spread polyamide in the shoulder portion 12 and the mouth portion 13 when the heating temperature of became. And, its oxygen permeability was 0.0042 cc / pkg · day. From this result, it can be understood that although high oxygen barrier properties are exhibited even when the MFR of the polyolefin is higher than 7 g / 10 min, higher oxygen barrier properties are exhibited when using a polyolefin of MFR lower than 7 g / 10 min.

Reference Signs List 10: laminated tube 11: body 12: shoulder 13: mouth 14: thread 15: cap 16: bottom 17: thread A: resin composition A1: metaxylylene group-containing polyamide A2: other resins 2A1B, 2C: Mold

Claims (5)

A laminate tube container in which a shoulder and a mouth are formed at one open end of a cylindrically formed trunk, wherein the shoulder and the mouth include a polyolefin and a metaxylylene group-containing polyamide In a laminate tube container composed of a composition,
The laminated tube container is characterized in that the polyamide is phase separated into a plane which spreads in a direction that hinders oxygen permeation from the outside to the inside of the laminated tube container.   The laminated tube container according to claim 1, wherein the resin composition contains a modified polyolefin in addition to the polyolefin and the metaxylylene group-containing polyamide.   The melt flow rate (MFR) of the said polyolefin is 3-7 g / 10min, The laminated tube container of Claim 1 or 2 characterized by the above-mentioned. A method of manufacturing a laminated tube container by forming a shoulder and an opening at one open end of a cylindrically formed trunk by a compression molding method, wherein the shoulder and the opening are made of polyolefin and In a method of producing a laminated tube container comprising a resin composition containing a metaxylylene group-containing polyamide,
The resin composition is kneaded with a screw in a cylinder while being heated, and supplied to one open end of the body through an adapter, and the resin composition thus supplied to the open end is compressed to form a shoulder. And forming the head and the mouth,
The method for producing a laminated tube container, wherein the heating temperature in the cylinder is equal to or lower than the melting start temperature of the metaxylylene group-containing polyamide.   The melt flow rate (MFR) of the said polyolefin is 3-7 g / 10min, The manufacturing method of the lamination tube container of Claim 4 characterized by the above-mentioned.

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