JPH11321896A - Synthetic-resin-made tube container having barrier properties - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the vapor barrier properties of a stretched blow tube container made of a single material, PET, and prevent moisture decrease from contents, by coating a specific surface area of an external face and/or internal face of a container main body, excepting a neck part, within an epoxy resin into a specific thickness. SOLUTION: A container main body 1 is formed in such a manner that a cold parison is formed out of polyester elastomer as its material, a biaxially stretched blow container is formed by biaxially stretched the parison, and also an epoxy resin layer 3 having a thickness of 5-80 μm is formed on 20-100% of the surface area of the internal face, external face, or both faces of the container, excepting a neck portion K. The epoxy resin as a coating agent is an oligomer resin having an epoxy group at the end whose molecular weight is approximately 300-10.000, and a glycidyl ether type or a glycidyl ester type, which is highly stable, is preferable. Further, in order to make the color of the epoxy resin invisible on the surface of the tube, the external face is printed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a biaxially stretch blow-molded tube container made of a polyester copolymer having excellent flexibility and elasticity and to improve the water vapor barrier property.

[0002]

2. Description of the Related Art Squeeze tube containers mainly made of plastic materials are widely used as containers for toothpastes, cosmetics, pharmaceuticals, foods, daily necessities, etc. because of their excellent flexibility, preservability of contents and portability. in use. The components of the contents to be stored in the plastic tube container include those in which oxygen in the air penetrates into the container and undergoes oxidative deterioration, and those with high permeability and high affinity with the tube material. A surfactant that significantly reduces the
It is known that solvents, oily fragrances and the like are contained.

[0003]

The stretch blow tube made of single-material PET is excellent in recyclability and appearance, but has a problem in that it cannot prevent weight loss of aqueous contents due to poor water vapor barrier properties. is there. Also, when the thickness is increased, the water vapor barrier property is improved, but the flexibility is poor, and there is a problem that the usability and usability are deteriorated. Therefore,
In the present invention, it is possible to improve the water vapor barrier property of the current single-material PET stretch blow tube container and provide a tube container without loss of moisture from the contents.
It is an object of the present invention to be able to distribute as food containers and to enable recycling of used containers.

[0004]

According to the present invention, there is provided a tube container comprising a combination of a container body and a cap fitted or screwed into a spout of the container body, wherein the container body comprises:
Aromatic polyester resin, thermoplastic polyester elastomer of aromatic polyester and aliphatic polyether,
A primary molded body of a cylindrical body molded by an injection molding method using any resin selected from thermoplastic polyester elastomers of an aromatic polyester and an aliphatic polyester as a molding raw material is biaxially formed in an axial direction and a radial direction. A container which is a secondary molded body obtained by integrally forming a shoulder portion and a body portion obtained by stretch blow molding, wherein 20 to 100% of the surface area of the outer surface and / or inner surface other than the neck portion of the container main body is epoxy. A synthetic resin barrier tube container coated with a system resin to a thickness of 5 μm to 80 μm, wherein a pattern print is applied to the outside of the portion coated with the epoxy resin, and a pigment or dye is added to the epoxy resin. The ink was added and printed, that is, the thermoplastic polyester elastomer which is a raw material for molding the primary molded body.
Crystalline melting point is 150 ℃ ~ 230 ℃, density 1.05~1.29g / cm ^3,
In addition, the flexural modulus is in the range of 100 to 9000 kg / cm ² , and the thickness of the body below the shoulder of the container as the secondary molded body is 80 to 800 μm.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to the drawings and the like. FIG. 1 shows (a) a front view, (b) an enlarged sectional view of a Y portion (outer coat), (c) an enlarged sectional view of an Y portion (inner coat), and (d) an enlarged Y portion of the barrier tube container of the present invention. It is sectional drawing (inner surface coating, outer surface printing), (e) Y part enlarged sectional view (outer surface coating and printing), (f) Y part enlarged sectional view (outer surface printing with epoxy resin ink). FIG.
Is a front view of the parison. The synthetic resin barrier tube container according to the present invention comprises a cold parison F as shown in FIG.
And the parison is biaxially stretched to form a biaxially stretched blow container as shown in FIG. 1 (a), and the epoxy resin layer 3 is coated on at least 20% of the inner surface, outer surface or both surfaces of the container. When the container main body 1 is provided and the container main body 1 is filled with contents, the container main body 1 and its neck K are screwed together with screws 4m and 4n to be in close contact with the mouth of the container main body 1. And a cap 2 for sealing.

This will be described in further detail. The stretched tube container molded with the polyester elastomer is inferior in water vapor barrier property in the container body 1 as it is, and when the liquid content is stored and stored for a long time, the side wall or the bottom of the container body 1 , And other liquid components such as moisture in the contents evaporate.
As a countermeasure, the present inventor has conducted intensive studies and as a result, in order to secure the water vapor barrier property of the container body 1, FIG.
As shown in (b), the outer surface of the container body 1 or FIG.
As shown in (c), it has been found that a water vapor barrier effect can be imparted by providing the epoxy resin-based resin layer 3 on the content storage section C side, that is, on the inner surface or both surfaces. However, the epoxy resin layer 3 has a problem in transparency,
Therefore, further experiments were repeated, and the thickness of the epoxy resin layer 3 was set to 3 to 80 μm.
By coating an epoxy resin on at least 20% of the total surface area of the inner surface, outer surface, or both inner and outer surfaces of the shoulder G and the same H excluding the above, it was possible to obtain a water vapor barrier property without any trouble in appearance. If the epoxy resin coating area is less than 20% of the total area, a necessary barrier property may not be obtained. The neck is thick and does not require any barrier treatment, and therefore does not require a coating in the present invention. When epoxy resin is coated on the inner surface of the container body 1, the content resistance is improved. This depends on the content resistance of the epoxy resin. The thickness of the epoxy resin layer 3 to be coated is 3 to 80 μm. The thickness of the epoxy resin layer 3 is 3 μm
If it is less than m, sufficient barrier properties will not be exhibited. On the other hand, if the thickness of the epoxy resin coating exceeds 80 μm, problems arise in the flexibility and flexibility of the tube container. The method of coating the epoxy resin in the synthetic resin barrier tube container according to the present invention can utilize an immersion method, a spray coating method, a roll coating method, a printing method, or the like, but is not limited to these methods. .

The present invention will be described in more detail. First, as an aromatic polyester resin used as a raw material for forming a cylindrical primary molded article (hereinafter referred to as cold parison) F in the present invention, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate,
It comprises a copolymer or a mixture of one or more polytetramethylene terephthalates.

More specifically, as the elastomer resin used for the cold parison F, a thermoplastic polyester elastomer having high flexibility is used. The thermoplastic polyester elastomer is an (AB) n-type multi-block copolymer, and has a crystalline high melting point polyester block unit (hard segment) and a low glass transition temperature (T
g) Copolymerization using a polybutylene terephthalate unit as a hard segment synthesized from an amorphous block unit (soft segment) and an aliphatic polyether unit such as poly (tetramethylene oxide) glycol (PTMG) as a soft segment. Aromatic polyester / aliphatic polyether type thermoplastic polyester elastomer, and aromatic polyester / fatty copolymerized with polybutylene terephthalate unit in the hard segment and aliphatic polyester such as polycaprolactone or polybutylene adipate in the soft segment Group III polyester type thermoplastic polyester elastomers are most suitable. As the resin physical properties of the thermoplastic polyester elastomer used, the crystalline melting point is 150 ° C. to 230 ° C., more preferably 18 ° C.
0 ° C. to 210 ° C., a density 1.05~1.29g / cm ^3, more preferably 1.10~1.20g / cm ^3, and flexural modulus 100 ~9000Kg / c
Thermoplastic polyester elastomers in the m ² , more preferably in the range of 1000-6000 kg / cm ² are preferred. When the crystal melting point is increased, the flexibility of the obtained tube container is deteriorated. Conversely, when the crystal melting point is lowered, the moldability of the cold parison molding resin is deteriorated.

As the density increases, the barrier properties, particularly the oxygen barrier properties, improve. However, the flexibility of the tube container deteriorates. When the density decreases, the barrier properties deteriorate significantly even when biaxially stretched. The elastic modulus is substantially proportional to the crystal melting point.

Next, the biaxial stretch blow molding of the tube container in the present invention will be described. Cold Parison F
Is heated to a temperature zone where the stretching effect is obtained, the shoulder is held by a shoulder support which is a part of the blow mold, and the body of the cold parison is positioned in the blow mold. An extension rod is inserted in the cold parison, and a passage for injecting pressure fluid is formed in the blow mold. In the state where the temperature of the cold parison F is in the temperature range where the stretching effect can be obtained, the stretching rod is advanced to perform uniaxial stretching in the axial direction, and air is injected into the body to stretch in the radial direction to perform biaxial stretch blow molding. I do. The stretching ratio depends on the thickness of the cold parison, but is preferably about 2 to 7 for both uniaxial and biaxial.

[0011] The semi-finished product of the blow tube container obtained in this biaxial stretching step can be made into a tube container having an open bottom by cutting an appropriate portion of the lower end serving as the bottom of the tube container. As a method for cutting the bottom of the tube container, a hot wire, an ultrasonic cutting method, or the like can be used in addition to a cutting method using a metal cutter.

The body portion has a high gas barrier property due to a biaxial stretching effect, and at the same time, transparency and surface smoothness are improved, and mechanical properties can be significantly improved. Also, when using a thermoplastic polyester elastomer as a molding resin, unlike conventional polyethylene terephthalate, the usability of the container,
In particular, since it becomes flexible, the squeezing property is remarkably improved, and the problem of the container remaining of the contents is solved.

Next, the epoxy resin coating on the tube container in the synthetic resin barrier tube container according to the present invention will be described in detail. Epoxy resin as a coating agent is an oligomeric resin having a molecular weight of about 300 to 10,000 having an epoxy group at a terminal, and depending on the type of production raw material, glycidyl ether type,
There are glycidyl ester type and glycidylamine type. The glycidylamine type has a nitrogen atom in the molecule, but other epoxy resins do not have a nitrogen atom. The glycidylamine type has poor stability and tends to gel at the stage of reaction with a curing agent. Therefore, a glycidyl ether type or glycidyl ester type having high stability is desirable.

Among these epoxy resins, the glycidyl ether type is an alcohol having an alcoholic hydroxyl group, or the phenol or glycidyl ester type is
It is obtained by epoxidizing active hydrogen-containing compounds having a carboxylic acid as a functional group with epichlorohydrin. Usually, the reaction is carried out in the presence of an alkali, and epoxidation is performed by a method of epoxidation in one reaction or two or more reactions.
In the reaction, a catalyst such as a tertiary amine, a quaternary amine, and triphenylphosphine can be used. Other methods include liquid-phase oxidation of a compound having a double bond with hydrogen peroxide or peracid, a method of air-oxidizing a compound having a double bond, and a method of using ylide, but are not limited thereto. Not a thing.

The reaction between bisphenol A and epichlorohydrin is based on 1 mole of bisphenol,
Epichlorohydrin requires at least 2 moles. Temperature is 5
It is generally carried out in the range of -150 ° C, but is not limited to this.

The reaction solvent may be any solvent capable of dissolving the raw materials, but preferably alcohols.
As the alcohols, in addition to lower alcohols such as methanol, ethanol, n-propanol and isopropanol, glycol ethers such as 2-methoxyethanol and 2-ethoxyethanol and polyhydric alcohols can be used.

The glycidyl ether type epoxy resin thus obtained includes, from its basic skeleton, bisphenol A type, bisphenol F type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol S
Type, bisphenol AF type, biphenyl type, naphthalene type, bifunctional epoxy resin having two epoxy groups in the molecule, phenol novolak type, orthocresol noorak type, DPP novolak type, Tris.
There is a multifunctional epoxy resin having three or more epoxy groups in a hydroxyphenylmethane type or tetraphenylolethane type molecule.

In addition to these aromatic epoxy resins, 1,2-ethanediol, 1,2-propanediol, 1,3-
Fats obtained by epoxidizing dihydric or higher aliphatic alcohols such as propanediol, 1,4-butanediol, 1,5-pentanediol, diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol with epichlorohydrin or dichlorohydrin. Group epoxy resins can also be used.

The glycidyl ester type epoxy resin can be obtained by reacting an aromatic or aliphatic carboxylic acid having two or more carboxyl groups (—COOH) in a molecule with epichlorohydrin or dichlorohydrin. Examples of the aromatic compound include phthalic acid, isophthalic acid, and epoxidized terephthalic acid. These epoxy resins may be used alone or as a mixture of two or more epoxy resins.

The epoxy resin has a molecular weight of 300 to 10,000 (number average molecular weight), a degree of polymerization (n) of 0.1 to 20, an epoxy equivalent of 100 to 10,000 g / eq, and a viscosity of 20 to 40,000 ps (25 ° C.).

As the curing agent to be reacted with the epoxy resin, polyaddition type polyamine, polyaddition type acid anhydride, polyaddition type polyphenol, polyaddition type polymercaptan, polyaddition type isocyanate, polyaddition type organic acid, catalyst type curing Agents, condensation-type curing agents, and the like. Among these, polyamine-based curing agents, organic acids and their derivatives (esters, acid anhydrides), which are highly reactive, are widely used, but are not particularly limited. As the polyamine, for example, diethylenetriamine, triethyleneamine, meta-xylylenediamine,
Unmodified polyamines such as isophorone diamine, 1,3-bisaminomethylcyclohexane, diaminodiphenylmethane, etc., modified polyamines such as polyamide, ketimine, epoxy modified zone (epoxy adduct), etc., and oxalic acid, phthalic acid, Maleic acid, hexahydrophthalic acid, pyromellitic acid, cyclopentadiene methylmaleic, dodecyl succinic acid, dichromaleic acid, chlorendic acid, or their esters, anhydrides and the like are not limited thereto. These curing agents cure the epoxy resin by combining one or more curing agents.

A three-dimensional crosslinked structure is formed in the resin film by the reaction between the curing agent and the epoxy resin, and the physical properties of the epoxy resin, particularly, mechanical strength, electrical properties, heat resistance, chemical resistance, adhesiveness, and the like. Gas barrier properties can be effectively improved.

The curing reaction of the epoxy resin is performed in a solvent. As the usable solvent, any solvent can be used as long as the epoxy resin and the curing agent are solubilized, and specifically, an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, an ester solvent, a ketone solvent, Alternatively, an alcohol solvent or the like can be used. The solvents may be used alone or as a mixture of two or more solvents. As alcohol solvents, glycol ethers such as 2-methoxyethanol and 2-ethoxyethanol and polyhydric alcohols can be used in addition to lower alcohols such as methanol, ethanol, n-propanol and isopropanol. The curing reaction is performed at room temperature or while heating. It is performed in the range of approximately 5 ° C to 150 ° C,
If the temperature is too high, a gelling reaction occurs, and the coating properties after the curing reaction deteriorate. If necessary, introduce a nitrogen stream into the reaction vessel to eliminate the effects of oxygen gas.

The amount of the curing agent to be added is arbitrarily selected depending on the number of epoxy groups in the epoxy resin. In the case of an acid anhydride, however, it also has catalytic curing, so that an epoxy equivalent of 0.1 to 0.5 is generally used. is there. However, the amount of the curing agent determines the three-dimensional structure and affects the physical properties of the cured film. Epoxy resins cured with a curing agent have the disadvantage that the resulting layers are somewhat brittle. In particular, in the present invention, since the adherend forming the film is a vapor-deposited film deposited, a resin film having a large flexural modulus has less curing. The following methods are available for imparting flexibility, but the method is not limited to these methods. Method of adding a plasticizer to leave a long-chain compound as an unreacted substance in the cured product. Plasticizer: Dibutyl phthalate, ester of organic acid ethylene glycol, adduct of tetrahydrofurfuryl alcohol with ethylene oxide. A method of adding a substance (flexibility imparting agent) that reacts the compound with an epoxy group A diluent is used. Diluent: butyl glycidyl ether, allyl glycidyl ether, diglycidyl ether, butanediol glycidyl ether, etc. Use a filler. Filler: mica powder, silica or quartz powder, calcium carbonate, alumina, zirconium citrate, iron oxide, glass powder Add plastic resin. Plastic resin: polyethylene, polypropylene, ethylene-vinyl acetate copolymer, acid-modified polyolefin,
Polyamide, etc.

When the epoxy resin is coated on the synthetic resin barrier tube container according to the present invention, the neck of the container body 1 is compared with the shoulder or the trunk of the tube container.
Since the polyester resin is thick and can exhibit a sufficient water vapor barrier property, a coating for improving the water vapor barrier property is unnecessary. Since the epoxy resin itself is colored, there is a problem that the coating portion does not become colorless and transparent. Therefore, by making the coating area 20% or more of the total surface area where the water vapor barrier property is improved, the water vapor barrier property can be improved without deteriorating the appearance. If the thickness of the epoxy resin is less than 3 μm, sufficient barrier properties may not be exhibited. Further, if the thickness of the epoxy resin layer exceeds 80 μm, problems occur in the flexibility and flexibility at the above.

The biaxially stretched tube container obtained in this manner is provided with an epoxy resin layer on at least 20% of the total area on the outer surface, the inner surface, or the inner and outer surfaces of the tube container. Even if the contents are filled and sealed and stored, liquid components including water in the contents do not evaporate through the wall of the container body, and can be used as a circulation container. Since the synthetic resin barrier tube container of the present invention uses a polyester resin as a raw material, it is possible to collect the used container and use the recycled polyester resin as a raw material for other purposes. The invention is also useful from the viewpoint of resource saving.

In order to prevent the color of the epoxy resin from appearing on the tube surface in the present invention, it can be solved by directly printing on the tube surface. Instead of the direct printing, a printed label may be affixed, or the tube container may be covered with a printed shrink film and heat shrunk to provide a picture.
For example, as shown in FIG. 1D, the inner surface of the tube may be coated with an epoxy resin 3 and the outer surface thereof may be printed 5. Further, as shown in FIG. 1E, a printing layer may be provided on the epoxy resin layer coated on the outer surface of the tube. Alternatively, a pigment or dye is added to an epoxy resin to form an ink, and the ink is used to perform printing 6 on the outer surface of the tube as shown in FIG.
Barrier properties can be imparted.

[0028]

[Example 1]

Resin used: Thermoplastic polyester elastomer Aromatic polyester / aliphatic polyether type elastomer (Toyobo perprene, P-40H) Density: 1.12 g / m ³ , Flexural modulus 520 kg / cm ² , Crystal melting point 172 ° C Injection molding of the resin A cold parison for a tube having a thread portion was formed from the preform shown in FIG.
The injection barrel temperature was 240 ° C. After the cold parison was heated and held at 90 ° C., a bottle-shaped molded body having a bottom having a body thickness of 0.3 mm and a body diameter of 35 mm shown in FIG. 2 was obtained by a biaxial stretch blow molding method. . Further, a part of the molded body (an area where the coating surface remains on the outer surface of the container except for the neck 20% even after the lower end is cut off) is immersed in a liquid tank containing the following coating A, and the thickness of the outer surface of the container is 5 μm ( After drying, heat-curing at a reaction temperature of 120 ° C for 1 hour,
The tube was cut horizontally by a metal cutter at a position 130 mm below the shoulder of the tube to obtain a tube shown in FIG. Coating agent A: 510 g of glycidyl ether derivative of bisphenol A is placed in a reaction vessel and 2 L of 1-ethoxy is added.
-2-Propanol was added, and the mixture was stirred with a magnetic stirrer while introducing nitrogen gas, and gradually dissolved at 80 ° C. After dissolution, while maintaining the temperature at 80 ° C., 1 L of n-propanol solution of triethylene tetramine at 83 ° C. was added, and the epoxy resin was cured while stirring with a magnetic stirrer. The reaction was carried out for 1 hour. After completion of the reaction, the temperature was raised to 120 ° C., the excess solvent was distilled off under reduced pressure, and a 5% solution (n-propanol) of an epoxy resin to which polyamine was added was prepared. [Embodiment 2] A bottle prepared by the method of Embodiment 1 was added to the bottle in the same manner as in Embodiment 1 except for the neck of the surface area of the outer surface.
%, Coated with the coating solution B shown below, cured at 110 ° C for 3 hours, and then cut horizontally with a metal cutter at a position 130 mm below the shoulder of the tube container. Obtained. Coating agent B: 550 g of glycidyl ether derivative of 1,4-butanediol is placed in a reaction vessel, 1 L of 2-butoxyethanol is added, and the mixture is stirred with a magnetic stirrer while introducing nitrogen gas. Dissolved. After dissolution, the temperature was increased to 100 ° C., and 55 g of hexahydrophthalic anhydride was added to 0.7 L of n-propanol solution, and the epoxy resin was cured while stirring with a magnetic stirrer. The reaction is carried out for 10 hours.
The temperature was raised to 0 ° C, the excess solvent was distilled off under reduced pressure, and a 7% solution (n-propanol) of an epoxy resin polymerized with a curing agent was prepared. [Example 3] After obtaining a bottle-shaped molded body having a bottomed part prepared by the method of Example 1, the outer surface area of the bottle was measured.
20% of coating liquid A is applied at a thickness of 76 μm, at 120 ° C.
After curing for 8 hours, 130m below the shoulder of the tube container
At the position of m, the tube was cut horizontally by a metal cutter to obtain a tube container. Example 4 A tube container was obtained in the same manner as in Example 1 except that the coating area of the epoxy resin was coated on 60% of the surface area of the inner surface and dried at 120 ° C. for 4 hours. Example 5 Example 1 was repeated except that PET resin J-120 (trade name, manufactured by Mitsui Chemicals, Inc.) was used as the resin to be used.
The same molding method and coating as described above were performed to obtain a tube container. [Comparative Example 1] A tube container was obtained without performing coating treatment on a bottle obtained in the same manner as in Example 1. <Water vapor barrier measurement> After the mouth portions of the tube containers of Examples 1 to 4 and Comparative Example 1 were thermally bonded with a laminated sealant containing an aluminum foil, a gas permeation measurement jig was attached to the bottom, and the gap was low. It was fixed with a molecular epoxy adhesive, and the water vapor permeability was measured by the MOCON method. The measurement conditions are as follows: Water vapor permeability: 40 ° C / 90% RH <Evaluation results>

[0029]

[Table 1] From Examples 1 to 5, it was found that by coating an epoxy resin on at least 20% of the surface area of the inner surface or the outer surface, the water vapor barrier property was improved. It has also been found that thickening the epoxy resin layer improves the barrier properties.

[0030]

EFFECT OF THE INVENTION The barrier tube tube made of synthetic resin of the present invention can significantly improve the water vapor barrier property of a biaxially stretched tube container made of a polyester resin, and can be used as a liquid container for long-term distribution. And could be. In addition, the coloring of the epoxy resin provided to improve the barrier properties also requires that the coating area be
By setting the content to 20 to 40%, necessary barrier properties could be secured without impairing the appearance of the container.

[Brief description of the drawings]

1 (a) is a front view of a barrier tube container of the present invention, (b) is an enlarged cross-sectional view of an Y section (outer coat), (c) is an enlarged cross-sectional view of an Y section (inner coat), and (d) is a Y section. Enlarged sectional view (inner coat, outer print), (e) Y section enlarged sectional view (outer coat and print), (f) Y section enlarged sectional view (external print with epoxy resin ink)

FIG. 2 is a front view of a parison.

[Explanation of symbols]

 F Parison P Barrier tube container x, y Stretching direction C Contents storage unit K Neck G Shoulder H Body 1 Container body 1w Polyester resin layer 2 Cap 3 Epoxy resin coating layer 3N Epoxy resin non-coating part 4m, 4n Screw 5 Printing 6 Epoxy resin ink

Claims (5)

[Claims] 1. A tube container comprising a combination of a container body and a cap fitted or screwed into a spout of the container body, wherein the container body is made of an aromatic polyester resin, or a thermosetting resin of an aromatic polyester and an aliphatic polyether. The primary molded body of a cylindrical body molded by an injection molding method using any resin selected from a thermoplastic polyester elastomer, a thermoplastic polyester elastomer of an aromatic polyester and an aliphatic polyester as a molding raw material, in an axial direction and a radial direction. A container which is a secondary molded body in which a shoulder portion and a body portion obtained by biaxially stretch blow molding in a direction are integrally formed, wherein the surface area of the outer surface and / or the inner surface other than the neck portion of the container body is 20 to 20%. 100% epoxy resin 5μm ~ 80μ
A barrier tube made of synthetic resin, characterized by being coated to a thickness of m. 2. A pattern printing is performed on the outside of the portion coated with the epoxy resin.
4. The barrier tube container made of a synthetic resin according to item 1. 3. The synthetic resin barrier tube container according to claim 1, wherein a pigment or a dye is added to the epoxy resin and printed as an ink. 4. The thermoplastic polyester elastomer, which is a raw material for molding the primary molded body, has a crystal melting point of 150 ° C. to 230 ° C.
° C, density 1.05 to 1.29 g / cm ³ , and flexural modulus 100
Plastic barrier tube container according to claims 1 to 3, characterized in that the range of ~9000Kg / cm ^2. 5. A barrier made of synthetic resin according to claim 1, wherein the thickness of the body below the shoulder of the container as the secondary molded body is 80 to 800 μm. Tube container.