KR102167086B1 - Internal films of container main body made of synthetic resin and manufacturing method thereof - Google Patents

Abstract

The present invention relates to an inner film of a synthetic resin container, and a method of manufacturing the inner film. According to the present invention, the inner film of a synthetic resin container includes: an ethylene vinyl alcohol copolymer (EVOH) film located on an upper portion of a container base material; a linear low-density polyethylene (LLDPE) film located on an upper portion of the EVOH film; and a low-density polyethylene (LDPE) film located on an upper portion of the LLDPE film. According to the above configuration, the present invention adheres a multilayer inner film to an inside of a container formed of a synthetic resin, so that excellent mechanical properties and excellent oxygen and odor barrier properties are obtained, and the contents accommodated in the container is able to be stably stored for a long period of time.

Description

Inner film of synthetic resin container and its manufacturing method {INTERNAL FILMS OF CONTAINER MAIN BODY MADE OF SYNTHETIC RESIN AND MANUFACTURING METHOD THEREOF}

The present invention relates to an inner film of a container made of synthetic resin and a method for manufacturing the same, and more particularly, by bonding a multilayered inner film to the inside of a container made of synthetic resin, it has excellent mechanical properties and excellent oxygen and odor barrier properties. It relates to an inner film of a container made of synthetic resin capable of stably storing the contents contained in the container for a long period of time and a method of manufacturing the same.

Various disposable containers can be found in everyday life, and disposable containers are being used more actively in food-related fields.

Among them, the most representative type of disposable containers using low-foaming synthetic resin is commonly used in places where various food ingredients are contained in marts and covered with wraps. The manufacturing process is simple, but the unit cost is low, and it has a light and excellent insulation effect. It is a kind with.

However, since the strength is weak and there is a lot of risk of being broken or damaged even with a small impact, the risk of damage during transportation is high in the case of finished products that have to go through a complicated distribution process, and they are gradually disappearing.

Polystyrene (PS) material is used as a means to solve this problem of strength, occupying most of the finished product market including various beverages, and now, polystyrene resin is used in delivery foods that used disposable containers using low foaming synthetic resin. Being replaced.

However, in the case of polystyrene, it is possible to manufacture it in a relatively thin thickness due to its strong strength, but there is a problem that the manufacturing cost is high and the function of insulation is small.

In addition, in food packaging containers, polyolefin-based films with excellent food stability and less harmful to the human body are mainly used, and polypropylene and polyethylene are generally used. In particular, polypropylene films are inexpensive and processable. It is widely used because of its excellent environmental friendliness. However, the polypropylene film has a disadvantage that it is difficult to use it alone in food packaging containers because it has low gas shielding properties due to its low crystallinity.

In order to solve the problem of low gas shielding property of the polypropylene film, a multilayer film in which a film having excellent gas shielding property is laminated between two polypropylene films has been used. As such a film having excellent gas shielding properties, a method of applying a material having excellent oxygen shielding properties, such as ethylene vinyl alcohol (EVOH), nylon, and a metal film, has been proposed. However, these materials must separately have an adhesive layer mixed with a polyolefin-based synthetic resin in order to improve adhesion to the polypropylene film.

In Korean Patent Laid-Open No. 10-2009-0032199, in addition to an oxygen barrier layer to prevent oxygen inflow, polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), ethylene vinyl alcohol (EVOH), and polyamide ) Or a food with improved oxygen shielding properties by additionally equipped with an oxygen absorbing layer in which an oxygen absorbing resin is added in a ratio of 10 to 80 wt% to a matrix resin selected from polyamide copolymers A packaging container is disclosed. However, manufacturing a multilayer sheet including such a plurality of layers requires a complicated process and causes an increase in cost.

Korean Patent Publication No. 10-2018-0047938 (published on May 10, 2018) Domestic registration patent No. 10-0187910 (registered on January 08, 1999) Domestic registered patent No. 10-0610290 (registered on August 1, 2006)

The present invention is an inner film of a synthetic resin container capable of stably storing contents contained in the container for a long period of time due to excellent mechanical properties and excellent oxygen and odor barrier properties by adhering a multi-layered inner film to the interior of a container made of synthetic resin, and It is to provide the manufacturing method.

Various problems to be solved by the present invention are not limited to the problems mentioned above, and other problems that are not mentioned will be clearly understood by those skilled in the art from the following description.

The inner film of the synthetic resin container according to the present invention includes an ethylene vinyl alcohol copolymer (EVOH) film positioned on the container substrate; Linear Low-Density Polyethylene (LLDPE) film positioned on the ethylene vinyl alcohol copolymer (EVOH) film; And a Low Density Polyethylene (LDPE) film positioned on the Linear Low-Density Polyethylene (LLDPE) film.

A first adhesive is formed between the container substrate and the EVOH film, a second adhesive is formed between the EVOH film and the LLDPE film, and a third adhesive is formed between the LDPE film and the LLDPE film. Ethylene Vinyl Alcohol Copolymer (EVOH) film, Linear Low-Density Polyethylene (LLDPE) film, and Low Density Polyethylene (LDPE) film may be adhered.

The third adhesive is prepared by including EVA resin (ethylene vinyl acetate resin; ETHYLENE VINYL ACETATE RESIN), acrylic emulsion resin and melamine resin, the third adhesive is EVA resin 10 to 15 parts by weight, acrylic emulsion resin 5 to 10 It may be included in a weight ratio of 15 to 20 parts by weight and 15 to 20 parts by weight of the melamine resin.

In addition, the method of manufacturing an inner film of a container made of synthetic resin according to the present invention comprises: preparing a container base material, applying a first adhesive on the container base material, and ethylene vinyl alcohol copolymer (Ethylene Vinyl Alcohol Copolymer) over the first adhesive material; EVOH) film is stacked, a second adhesive is applied on the ethylene vinyl alcohol copolymer (EVOH) film, and a linear low-density polyethylene (LLDPE) film is applied on the second adhesive Is laminated, a third adhesive is applied on the linear low-density polyethylene (LLDPE) film, a low density polyethylene (LDPE) film is laminated on the third adhesive, and the container substrate , First adhesive, ethylene vinyl alcohol copolymer (EVOH) film, second adhesive, linear low-density polyethylene (LLDPE) film, third adhesive and linear low-density polyethylene (Linear Low-Density) Films made of polyethylene (LLDPE) films are thermocompressed, and the thermocompressed films are formed.

The container substrate, first adhesive, ethylene vinyl alcohol copolymer (EVOH) film, second adhesive, linear low-density polyethylene (LLDPE) film, third adhesive and linear low-density polyethylene (Linear Thermocompression bonding of films made of Low-Density Polyethylene; LLDPE) films can be performed by pressing for 5 to 20 minutes at a temperature of 120 to 130 °C at a pressure of 3 to 5 kgf/cm ² and then cooling for 10 to 30 minutes. .

The third adhesive is prepared by including EVA resin (ethylene vinyl acetate resin; ETHYLENE VINYL ACETATE RESIN), acrylic emulsion resin and melamine resin, the third adhesive is EVA resin 10 to 15 parts by weight, acrylic emulsion resin 5 to 10 It may be included in a weight ratio of 15 to 20 parts by weight and 15 to 20 parts by weight of the melamine resin.

Details of other embodiments are included in the detailed description.

The inner film of the container made of synthetic resin according to the present invention adheres a multi-layered inner film to the inside of the container made of synthetic resin, so that it has excellent mechanical properties and excellent oxygen and odor barrier properties, so that the contents contained in the container can be stably stored for a long time. have.

It will be fully understood that the embodiments of the technical idea of the present invention can provide various effects not specifically mentioned.

1 is a view schematically showing a cross-section of a container made of synthetic resin in which an inner film is formed according to the present invention.
FIG. 2 is an enlarged view of part A of FIG. 1 and schematically showing a cross section of an inner film of a container made of synthetic resin according to the present invention.

Advantages and features of the present invention, and a method of achieving them will become apparent with reference to the embodiments described below in detail. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosed content may be thorough and complete, and the spirit of the present invention may be sufficiently conveyed to those skilled in the art.

The terms used in the present application are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise.

Unless otherwise defined, all terms including technical or scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. Terms such as those defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning of the related technology, and should not be interpreted as an ideal or excessively formal meaning unless explicitly defined in this application. Does not.

Hereinafter, a preferred embodiment will be described in detail with respect to the inner film of the container made of synthetic resin according to the present invention with reference to the accompanying drawings.

1 is a view schematically showing a cross-section of a synthetic resin container in which an inner film is formed according to the present invention, and FIG. 2 is an enlarged view of part A of FIG. It is a drawing shown.

1 and 2, the inner film 10 of the container made of synthetic resin according to the present invention is an ethylene vinyl alcohol copolymer (EVOH) film 200 positioned on the container substrate 100, Linear Low-Density Polyethylene (LLDPE) film 300 and the Linear Low-Density Polyethylene (LLDPE) film 300 positioned on the Ethylene Vinyl Alcohol Copolymer (EVOH) film 200; LLDPE) includes a low-density polyethylene (LDPE) film 400 positioned on the film 300.

The container substrate 100 is molded into a conventional container to accommodate beverages and the like therein, and may be made of synthetic resin. For example, the container base material 100 may be formed of polyethylene terephthalate (PET) material, and the container base material 100 protects contents such as beverages contained therein from external impact. I can.

The ethylene vinyl alcohol copolymer (EVOH) film 200 is located on the surface of the container substrate 100, and the EVOH film 200 is a copolymer material of ethylene and vinyl acetate, and has oxygen and retention properties. It has excellent barrier properties and is widely used for food packaging. In addition, the EVOH film 200 has excellent moldability even at low temperatures along with the replacement of the gas barrier (GAS Barrier) of the existing aluminum foil and improvement of opaque properties, as well as harmful substances generated during decomposition. It is also effective in improving environmental problems.

The linear low-density polyethylene (LLDPE) film 300 has a molecular structure smaller than that of a general LDPE (Low Density Polyethylene) film, and has a molecular weight distribution similar to that of HDPE, and when heated. The melt viscosity is relatively high.

In addition, since the LLDPE film 300 has better crystallinity than normal low-density polyethylene (LDPE), it has good stiffness and scratch properties, and has a large tear resistance and a relatively large surface hardness, so that a molded article having good gloss can be obtained.

The low-density polyethylene (LDPE) film 400 is a synthetic resin made of monomer ethylene and has excellent water resistance, chemical resistance, and electrical insulation, and is used as a packaging material, insulation, sound-absorbing material, cable insulator, and the like. In addition, the LDPE film 400 has excellent impact strength, flexibility, film transparency, particularly tensile and shrinkage, as well as impact resistance and easy processability.

A first adhesive (not shown) is formed between the container base material 100 and the EVOH film 200, and the first adhesive may adhere the EVOH film 200 and the container base material 100. 1 The adhesive is blended in a weight ratio of 40 to 80 parts by weight of acrylic emulsion resin, 20 to 30 parts by weight of ethylene glycol, 10 to 20 parts by weight of isocyanate, and 5 to 15 parts by weight of phosphorus monomer, and then added to the mixing tank. It can be prepared by mixing.

The acrylic emulsion resin has a low film formation temperature and excellent flexibility even without the use of a plasticizer, and has excellent weather resistance and abrasion resistance.The acrylic emulsion resin is prepared including a monomer composition, a crosslinkable monomer and a stabilizer, The acrylic emulsion resin may be prepared including 4 to 8 parts by weight of the crosslinkable monomer and 0.1 to 0.5 parts by weight of a stabilizer based on 100 parts by weight of the monomer composition.

The monomer composition may be any one or more monomers selected from the group consisting of alkenyl aromatic monomer, acrylonitrile, vinyl acetate, and vinyl versatate, and the The crosslinkable monomer plays a role of imparting a crosslinking function to the acrylic emulsion resin, and can improve the adhesion of the acrylic emulsion resin. The crosslinkable monomer is a hydroxy functional monomer, an amino functional monomer. Any one or more selected from the group consisting of a monomer, an epoxy functional monomer, a carbonyl functional monomer, and a methylol functional monomer may be used.

The hydroxy functional monomer may be any one or more monomers selected from the group consisting of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxybutyl acrylate, and the amino functional monomer is N ,N-dimethyl aminoethyl methacrylate, N,N-dimethyl aminoethyl acrylate, and N,tert-butyl aminoethyl methacrylate may be used any one or more monomers selected from the group consisting of, the epoxy functional monomer may be used glycidyl methacrylate, the car The bonyl functional monomer may be any one or more monomers selected from diacetone acrylamide or acetoacetoxyrthyl metacrylate, and the methylol functional monomer is any one or more monomers selected from the group consisting of N-methylol acrylamide, N-methylol methacrylamide and Nn-isobutoxymethyl acrylamide Can be used.

The stabilizer is added to improve the physical and chemical stability of the acrylic emulsion resin, and the stabilizer may be any one selected from allyl alkyl sulfonate or copolymerizable sulfonate manomer.

The ethylene glycol may be added to improve fluidity and workability before curing, and to improve physical and chemical performance after curing.

In the present invention, the ethylene glycol may be contained in an amount of 20 to 30 parts by weight, and when the ethylene glycol is contained in an amount of less than 20 parts by weight, the effect of adding the ethylene glycol may not be sufficiently exhibited, and 30 parts by weight If it is included in excess, the overall physical properties of the first adhesive may be deteriorated because the overall physical properties are not balanced.

The isocyanate acts as a curing agent, for example, the isocyanate is hexamethylene diisocyanate (HDI), hexamethylene diisocyanate trimer (HDT), isophorone diisocyanate (Isophorone Diisocyanate, IPDI), and cyclohexylmethane. Any one or more selected from the group consisting of diisocyanate (Cyclohexylmethanediisocyanate, H12MDI) may be used.

The phosphorus monomer may be used to improve the adhesion of the EVOH film to the container. For example, the phosphorus monomer is bis[2-(methacyloyloxy)ethyl] phosphate (Bis[2-(methacyloyloxy)). ethyl] phosphate, DMEP), 2-(methacryloyloxy) ethyl phosphate (2-(methacryloyloxy) ethyl phosphate, MMEP) and Tris(2-methacryloyloxy)ethyl phosphate (TMEP) Any one or more selected from the group consisting of may be used.

A second adhesive (not shown) is formed between the EVOH film 200 and the LLDPE film 300, and the second adhesive may adhere the LLDPE film 300 and the EVOH film 200. 2 The adhesive is blended in a weight ratio of 30 to 60 parts by weight of a self-emulsifying epoxy resin, 20 to 40 parts by weight of an acrylic modified polyester resin, 10 to 20 parts by weight of a filler, and 5 to 15 parts by weight of a curing agent, and then added to the mixing tank. It can be prepared by mixing.

The self-emulsifying epoxy resin is an epoxy resin having an active group capable of emulsifying in itself, and the self-emulsifying epoxy resin is a self-emulsifying modified epoxy resin having an epoxy equivalent of 200 to 230 g/eq. Physical properties such as strength, weather resistance, and water resistance can be remarkably improved.

The self-emulsifying type epoxy resin is used in 30 to 60 parts by weight.If the self-emulsifying type epoxy resin is included in less than 30 parts by weight, adhesion and sealing properties may be deteriorated, and when it is included in more than 60 parts by weight, drying properties This delay can occur.

The acrylic-modified polyester resin is condensed and polymerized with a polybasic acid containing 40 to 50% by weight of anhydrous acid and 50 to 60% by weight of an aliphatic acid by condensation polymerization of a polyhydric alcohol containing 80 to 90% by weight of a diol and 10 to 20% by weight of a triol. To prepare a polyester resin having a value of 45 to 65 mgKOH/g, an acid value of 3 mgKOH/g or less, a glass transition temperature of 5 to 20°C, and a weight average molecular weight (Mw) of 2,500 to 3,500, and the polyester resin 50 to 60 weight % And 40-50% by weight of acrylic monomer are grafted to have a weight average molecular weight (Mw) of 5,000 to 7,000, a hydroxyl value of 50 to 60 mgKOH/g, an acid value of 3 mgKOH/g or less, and a glass transition temperature of 10 to 20°C An acrylic modified polyester resin in the range can be prepared.

The filler is added to improve the thermal and physical strength of the inner film, prevent wear and tear, and improve corrosion resistance and weather resistance.For example, the filler includes perlite, vermiculite, Any one or more selected from the group consisting of barite, talc, diatomaceous earth, graphite, silica and calcium carbonate is used, and the average particle diameter is preferably 0.1 to 3 μm.

The curing agent is included in the second adhesive and performs a function of curing, and the curing agent may be used by mixing a curing agent resin and a curing accelerator.

Modified aliphatic polyamine may be used as the curing agent resin, and 2,4,6-tridimethylaminomethyl phenol may be used as the curing accelerator, and the curing agent resin and the curing accelerator are 10 to 20 parts by weight of the curing agent resin, respectively And the curing accelerator may be mixed in a weight ratio of 1 to 5 parts by weight.

A third adhesive (not shown) is formed between the LDPE film 400 and the LLDPE film 300, and the third adhesive may adhere the LDPE film 400 and the LLDPE film 300. 3 The adhesive is prepared by including EVA resin (ethylene vinyl acetate resin; ETHYLENE VINYL ACETATE RESIN), acrylic emulsion resin and melamine resin, but the third adhesive is 10 to 15 parts by weight of EVA resin, 5 to 10 parts by weight of acrylic emulsion resin And it may be included in a weight ratio of 15 to 20 parts by weight of the melamine resin.

For example, the acrylic emulsion resin is prepared by synthesizing 2EHAM (2ethylhexyl acrylate monomer) and BAM (acrylate normal butyl ester; BUTYL ACRYLATE MONOMER) in a weight ratio of 3:1, and the melamine resin is 35 to 40 To prepare a mixed solution of 25 to 35 parts by weight of melamine, 15 to 35 parts by weight of formaldehyde, 15 to 25 parts by weight of water, 1 to 3 parts by weight of diethylene glycol, and 0.5 to 2 parts by weight of sodium hydroxide at a temperature of °C. Then, after adjusting the pH of the mixed solution to 7.8 to 8.3, the mixed solution was subjected to a polymerization reaction at a temperature of 90 to 95°C for 1 to 3 hours, the polymerized reaction product was cooled to 35 to 40°C, and the pH was adjusted to 7.2. To 7.7 to 1 to 5 parts by weight of (5-Ethyl-2-methyl-1,3,2-dioxaphosphorinan-5-yl)methyl dimethyl phosphonate P in the cooled reactant based on 100 parts by weight of the cooled reactant. It can be prepared by adding -oxide.

Hereinafter, a preferred embodiment will be described in detail with respect to a method of manufacturing an inner film of a container made of synthetic resin according to the present invention with reference to the accompanying drawings.

First, the container substrate 100 may be prepared.

For example, the container base material 100 may be formed of polyethylene terephthalate (PET) material, and the container base material 100 protects contents such as beverages contained therein from external impact. I can.

Next, a first adhesive may be applied to the top of the container substrate 100.

The first adhesive is mixed in a weight ratio of 40 to 80 parts by weight of an acrylic emulsion resin, 20 to 30 parts by weight of ethylene glycol, 10 to 20 parts by weight of isocyanate, and 5 to 15 parts by weight of a phosphorus monomer, and then added to the mixing tank. It can be prepared by mixing uniformly.

Next, an ethylene vinyl alcohol copolymer (EVOH) film 200 may be stacked on the first adhesive.

The EVOH film 200 is a copolymer material of ethylene and vinyl acetate, and is widely used for food packaging because of its excellent oxygen and retention (scent) barrier properties. In addition, the EVOH film 200 has excellent moldability even at low temperatures along with the replacement of the gas barrier (GAS Barrier) of the existing aluminum foil and improvement of opaque properties, as well as harmful substances generated during decomposition. It is also effective in improving environmental problems.

Subsequently, a second adhesive may be applied on the EVOH film 200.

The second adhesive is blended in a weight ratio of 30 to 60 parts by weight of a self-emulsifying epoxy resin, 20 to 40 parts by weight of an acrylic modified polyester resin, 10 to 20 parts by weight of a filler, and 5 to 15 parts by weight of a curing agent and added to the mixing tank. It can be prepared by uniformly mixing after.

Next, a linear low-density polyethylene (LLDPE) film 300 may be laminated on the second adhesive.

Since the crystallinity of the LLDPE film 300 is generally better than that of low-density polyethylene (LDPE), it has good stiffness and scratch properties, and has a relatively large surface hardness due to high tear resistance, so that a molded article having good gloss can be obtained.

Next, a third adhesive may be applied on the LLDPE film 300.

The third adhesive is prepared by including EVA resin (ethylene vinyl acetate resin; ETHYLENE VINYL ACETATE RESIN), acrylic emulsion resin and melamine resin, the third adhesive is EVA resin 10 to 15 parts by weight, acrylic emulsion resin 5 to 10 It may be included in a weight ratio of 15 to 20 parts by weight and 15 to 20 parts by weight of the melamine resin.

Subsequently, a Low Density Polyethylene (LDPE) film 400 may be laminated on the third adhesive.

The LDPE film 400 has excellent impact strength, flexibility, film transparency, particularly tensile and shrinkage, as well as impact resistance and easy processability.

Next, a film made of the container substrate 100, the first adhesive, the EVOH film 200, the second adhesive, the LLDPE film 300, the third adhesive, and the LDPE film 400 may be thermally compressed.

The thermocompression bonding is performed in a film made of the container substrate 100, the first adhesive, the EVOH film 200, the second adhesive, the LLDPE film 300, the third adhesive and the LDPE film 400 at a temperature of 120 to 130°C. It can be carried out by pressing for 5 to 20 minutes at a pressure of 3 to 5 kgf/cm ² and then cooling at room temperature for 10 to 30 minutes.

Next, a film made of the heat-compressed container substrate 100, the first adhesive, the EVOH film 200, the second adhesive, the LLDPE film 300, the third adhesive and the LDPE film 400 is formed to Can be manufactured.

A method of manufacturing a container by molding a film made of the thermocompressed container substrate 100, the first adhesive, the EVOH film 200, the second adhesive, the LLDPE film 300, the third adhesive and the LDPE film 400 As examples, there are various methods such as injection molding and compression molding, which are known techniques to those of ordinary skill in the art. For convenience of explanation and clarity of the technical idea of the present invention, Description will be omitted.

Hereinafter, a preferred embodiment of the inner film of the container made of synthetic resin according to the present invention will be described in more detail.

<Example>

First, after preparing a film consisting of a container substrate (PET material film), a first adhesive, an EVOH film, a second adhesive, an LLDPE film, a third adhesive, and an LDPE film, the film is 4kgf/cm ² at a temperature of 120 to 130°C. Pressurized for 10 minutes at a pressure of, and then cooled at room temperature for 20 minutes.

Next, the cooled container base material, the first adhesive, the EVOH film, the second adhesive, the LLDPE film, the third adhesive and the film consisting of the LDPE film was injection-molded to prepare a synthetic resin bottle container with an inner film attached thereto.

<Comparative Example 1>

A synthetic resin bottle container was manufactured in a similar manner to the Example. In Comparative Example 1, a film made of a container substrate, a first adhesive, and an EVOH film was formed to prepare a synthetic resin bottle container with an inner film attached thereto.

<Comparative Example 2>

Without forming an inner film, a PET film was molded to prepare a synthetic resin bottle container.

The adhesiveness and gas shielding properties were evaluated as follows using the synthetic resin bottle containers prepared according to the above Examples and Comparative Examples 1 and 2, and the results are shown in Table 1 below.

(1) adhesion evaluation

A portion of the synthetic resin bottle container manufactured according to the above Examples and Comparative Examples was cut into 10 * 10 cm, and maintained for 30 minutes at 85° C., and then delamination was visually confirmed.

O: No delamination phenomenon

△: Within 5mm of peeling of the outermost part

X: peeling of the outermost part exceeds 5mm

(2) Gas shielding evaluation

After putting 5 g of rice in the synthetic resin bottle container manufactured according to the above Examples and Comparative Examples, sealed packaging so that there is no flow of moisture and gas, and left to stand for 20 days in an atmosphere of 50°C and 65% relative humidity, and then opened to determine whether there is corruption. Was confirmed.

O: No corruption

X: There is corruption

division Example Comparative Example 1 Comparative Example 2 Adhesiveness O △ O Gas shielding O X X

Referring to [Table 1], it was confirmed that the synthetic resin bottle container with the inner film attached according to the examples was superior to both the adhesiveness and gas shielding properties compared to the synthetic resin bottle container according to the comparative examples.

In the above, a preferred embodiment of the present invention has been described, but those of ordinary skill in the art to which the present invention pertains will understand that the present invention can be implemented in other specific forms without changing the technical spirit or essential features. I will be able to. Therefore, it should be understood that the exemplary embodiment described above is illustrative in all respects and is not limiting.

10; Inner film 100; Container description
200; EVOH film 300; LLDPE film
400; LDPE film

Claims (6)

An ethylene vinyl alcohol copolymer (EVOH) film positioned on the container substrate;
Linear Low-Density Polyethylene (LLDPE) film positioned on the ethylene vinyl alcohol copolymer (EVOH) film; And
Including a low-density polyethylene (LDPE) film positioned on the linear low-density polyethylene (LLDPE) film,
A first adhesive is formed between the container substrate and the EVOH film, a second adhesive is formed between the EVOH film and the LLDPE film, and a third adhesive is formed between the LDPE film and the LLDPE film. Attaching an Ethylene Vinyl Alcohol Copolymer (EVOH) film, a Linear Low-Density Polyethylene (LLDPE) film, and a Low Density Polyethylene (LDPE) film,
The first adhesive is mixed in a weight ratio of 40 to 80 parts by weight of an acrylic emulsion resin, 20 to 30 parts by weight of ethylene glycol, 10 to 20 parts by weight of isocyanate, and 5 to 15 parts by weight of a phosphorus monomer, and then added to the mixing tank. Prepared by mixing, the acrylic emulsion resin is prepared by containing 4 to 8 parts by weight of a crosslinkable monomer and 0.1 to 0.5 parts by weight of a stabilizer based on 100 parts by weight of the monomer composition, and the monomer composition is an alkenyl aromatic monomer (alkenyl aromatic monomer (alkenyl aromatic monomer), acrylonitrile, vinyl acetate, and vinyl versatate, and any one or more monomers selected from the group consisting of vinyl versatate is used, and the crosslinkable monomer is a hydroxy functional monomer , Amino (amino) functional monomer, epoxy (epoxy) functional monomer, carbonyl (carbonyl) functional monomer and methylol (methyol) any one or more selected from the group consisting of a functional monomer is used, the stabilizer is allyl alkyl sulfate (allyl alkyl sulfonate) or a copolymerizable sulfonate manomer is used, and the isocyanate is hexamethylene diisocyanate (HDI), hexamethylene diisocyanate trimer (HDT), isophorone diisocyanate ( Isophorone Diisocyanate, IPDI) and at least one selected from the group consisting of cyclohexylmethanediisocyanate (H12MDI) is used, and as the phosphorus monomer, bis[2-(methacryloxy)ethyl] phosphate (Bis[2-( methacyloyloxy)ethyl] phosphate, DMEP), 2-(methacryloxy)ethylphosphate (2-(me thacryloyloxy) ethyl phosphate, MMEP) and tris 2-(methacryloyloxy) ethyl phosphate (Tris(2-methacryloyloxy) ethyl phosphate, TMEP) is used,
The second adhesive is blended in a weight ratio of 30 to 60 parts by weight of a self-emulsifying epoxy resin, 20 to 40 parts by weight of an acrylic modified polyester resin, 10 to 20 parts by weight of a filler, and 5 to 15 parts by weight of a curing agent and added to the mixing tank. It is prepared by mixing after, but the self-emulsifying epoxy resin is a self-emulsifying modified epoxy resin having an epoxy equivalent of 200 to 230 g/eq, and the acrylic modified polyester resin is 80 to 90% by weight of diol and 10 to 20 of triol Condensation polymerization of a polyhydric alcohol containing% by weight with a polybasic acid containing 40 to 50% by weight of anhydric acid and 50 to 60% by weight of an aliphatic acid to obtain a hydroxyl value of 45 to 65 mgKOH/g, an acid value of 3 mgKOH/g or less, and a glass transition temperature A polyester resin having a weight average molecular weight (Mw) of 5 to 20°C and a weight average molecular weight (Mw) of 2,500 to 3,500 was prepared, and 50 to 60 wt% of the polyester resin and 40 to 50 wt% of an acrylic monomer were grafted to form a weight average molecular weight ( Mw) 5,000 to 7,000, a hydroxyl value of 50 to 60 mgKOH/g, an acid value of 3 mgKOH/g or less, and an acrylic modified polyester resin having a glass transition temperature in the range of 10 to 20°C is used, and the filler is perlite , Vermiculite, barite, talc, diatomaceous earth, graphite, silica, and calcium carbonate. Any one or more selected from the group consisting of is used, and the average particle diameter is 0.1 to 3 μm. ,
The third adhesive is prepared by including EVA resin (ethylene vinyl acetate resin; ETHYLENE VINYL ACETATE RESIN), acrylic emulsion resin and melamine resin, the third adhesive is EVA resin 10 to 15 parts by weight, acrylic emulsion resin 5 to 10 It is included in a weight ratio of 15 to 20 parts by weight of a melamine resin, and the acrylic emulsion resin contains 2EHAM (2ethylhexyl acrylate monomer) and BAM (acrylate normal butyl ester; BUTYL ACRYLATE MONOMER) in a weight ratio of 3:1. It is synthesized and prepared, and the melamine resin is 25 to 35 parts by weight of melamine, 15 to 35 parts by weight of formaldehyde, 15 to 25 parts by weight of water, 1 to 3 parts by weight of diethylene glycol and 0.5 to sodium hydroxide at a temperature of 35 to 40°C. After preparing a mixed solution mixed at a weight ratio of 2 parts by weight and adjusting the pH of the mixed solution to 7.8 to 8.3, the mixed solution was subjected to polymerization reaction at a temperature of 90 to 95°C for 1 to 3 hours, and the polymerized After cooling the reactant to 35 to 40 °C and adjusting the pH to 7.2 to 7.7, 1 to 5 parts by weight of (5-Ethyl-2-methyl-1,3,) based on 100 parts by weight of the cooled reactant in the cooled reactant. Inner film of a synthetic resin container, characterized in that prepared by adding 2-dioxaphosphorinan-5-yl)methyl dimethyl phosphonate P-oxide.
delete delete Prepare the container base,
Applying a first adhesive on the top of the container substrate,
Laminating an ethylene vinyl alcohol copolymer (EVOH) film on the first adhesive,
Applying a second adhesive on the ethylene vinyl alcohol copolymer (Ethylene Vinyl Alcohol Copolymer; EVOH) film,
Laminating a linear low-density polyethylene (LLDPE) film on top of the second adhesive,
Applying a third adhesive on the top of the linear low-density polyethylene (LLDPE) film,
Laminating a Low Density Polyethylene (LDPE) film on the third adhesive,
The container substrate, first adhesive, ethylene vinyl alcohol copolymer (EVOH) film, second adhesive, linear low-density polyethylene (LLDPE) film, third adhesive and linear low-density polyethylene (Linear Films made of Low-Density Polyethylene; LLDPE) are thermocompressed,
Forming the thermocompressed films,
The container substrate, first adhesive, ethylene vinyl alcohol copolymer (EVOH) film, second adhesive, linear low-density polyethylene (LLDPE) film, third adhesive and linear low-density polyethylene (Linear The thermocompression bonding of films made of Low-Density Polyethylene; LLDPE) films is performed by pressing for 5 to 20 minutes at a temperature of 120 to 130°C at a pressure of 3 to 5 kgf/cm ² and then cooling for 10 to 30 minutes,
The first adhesive is mixed in a weight ratio of 40 to 80 parts by weight of an acrylic emulsion resin, 20 to 30 parts by weight of ethylene glycol, 10 to 20 parts by weight of isocyanate, and 5 to 15 parts by weight of a phosphorus monomer, and then added to the mixing tank. Prepared by mixing, the acrylic emulsion resin is prepared by containing 4 to 8 parts by weight of a crosslinkable monomer and 0.1 to 0.5 parts by weight of a stabilizer based on 100 parts by weight of the monomer composition, and the monomer composition is an alkenyl aromatic monomer (alkenyl aromatic monomer (alkenyl aromatic monomer), acrylonitrile, vinyl acetate, and vinyl versatate, and any one or more monomers selected from the group consisting of vinyl versatate is used, and the crosslinkable monomer is a hydroxy functional monomer , Amino (amino) functional monomer, epoxy (epoxy) functional monomer, carbonyl (carbonyl) functional monomer and methylol (methyol) any one or more selected from the group consisting of a functional monomer is used, the stabilizer is allyl alkyl sulfate (allyl alkyl sulfonate) or a copolymerizable sulfonate manomer is used, and the isocyanate is hexamethylene diisocyanate (HDI), hexamethylene diisocyanate trimer (HDT), isophorone diisocyanate ( Isophorone Diisocyanate, IPDI) and at least one selected from the group consisting of cyclohexylmethanediisocyanate (H12MDI) is used, and as the phosphorus monomer, bis[2-(methacryloxy)ethyl] phosphate (Bis[2-( methacyloyloxy)ethyl] phosphate, DMEP), 2-(methacryloxy)ethylphosphate (2-(me thacryloyloxy) ethyl phosphate, MMEP) and tris 2-(methacryloyloxy) ethyl phosphate (Tris(2-methacryloyloxy) ethyl phosphate, TMEP) is used,
The second adhesive is blended in a weight ratio of 30 to 60 parts by weight of a self-emulsifying epoxy resin, 20 to 40 parts by weight of an acrylic modified polyester resin, 10 to 20 parts by weight of a filler, and 5 to 15 parts by weight of a curing agent and added to the mixing tank. It is prepared by mixing after, but the self-emulsifying epoxy resin is a self-emulsifying modified epoxy resin having an epoxy equivalent of 200 to 230 g/eq, and the acrylic modified polyester resin is 80 to 90% by weight of diol and 10 to 20 of triol Condensation polymerization of a polyhydric alcohol containing% by weight with a polybasic acid containing 40 to 50% by weight of anhydrous acid and 50 to 60% by weight of an aliphatic acid, so that the hydroxyl value is 45 to 65 mgKOH/g, the acid value is 3 mgKOH/g or less, and the glass transition temperature is A polyester resin having a weight average molecular weight (Mw) of 5 to 20°C and a weight average molecular weight (Mw) of 2,500 to 3,500 was prepared, and 50 to 60 wt% of the polyester resin and 40 to 50 wt% of an acrylic monomer were grafted to form a weight average molecular weight ( Mw) 5,000 to 7,000, a hydroxyl value of 50 to 60 mgKOH/g, an acid value of 3 mgKOH/g or less, and an acrylic modified polyester resin having a glass transition temperature in the range of 10 to 20°C is used, and the filler is perlite , Vermiculite, barite, talc, diatomaceous earth, graphite, silica, and calcium carbonate. Any one or more selected from the group consisting of is used, and the average particle diameter is 0.1 to 3 μm. ,
The third adhesive is prepared by including EVA resin (ethylene vinyl acetate resin; ETHYLENE VINYL ACETATE RESIN), acrylic emulsion resin and melamine resin, the third adhesive is EVA resin 10 to 15 parts by weight, acrylic emulsion resin 5 to 10 It is included in a weight ratio of 15 to 20 parts by weight of a melamine resin, and the acrylic emulsion resin contains 2EHAM (2ethylhexyl acrylate monomer) and BAM (acrylate normal butyl ester; BUTYL ACRYLATE MONOMER) in a weight ratio of 3:1. It is synthesized and prepared, and the melamine resin is 25 to 35 parts by weight of melamine, 15 to 35 parts by weight of formaldehyde, 15 to 25 parts by weight of water, 1 to 3 parts by weight of diethylene glycol and 0.5 to sodium hydroxide at a temperature of 35 to 40°C. After preparing a mixed solution mixed at a weight ratio of 2 parts by weight and adjusting the pH of the mixed solution to 7.8 to 8.3, the mixed solution was subjected to polymerization reaction at a temperature of 90 to 95°C for 1 to 3 hours, and the polymerized After cooling the reactant to 35 to 40 °C and adjusting the pH to 7.2 to 7.7, 1 to 5 parts by weight of (5-Ethyl-2-methyl-1,3,) based on 100 parts by weight of the cooled reactant in the cooled reactant. 2-dioxaphosphorinan-5-yl)methyl dimethyl phosphonate P-oxide is added to prepare an inner film of a synthetic resin container. delete delete

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