KR20030023893A - Laminated tube having plastic multi-layer film structure and method for preparing the same - Google Patents

Abstract

PURPOSE: A laminate tube having a plastic multilayer film structure is provided, which has a multilayer film construction composed of only the plastic materials having the good resilience as well as the gas and flavor shielding property. Also, a preparation method thereof is provided. CONSTITUTION: The laminate tube having the plastic multilayer film structure comprises: the inner surface layer(11) constituting the interior of tube, a first adhesive layer(12a), a first shielding layer(13a) to prevent the gas(oxygen) and moisture from permeating into tube, a second adhesive layer(12b), a support layer(14), a third adhesive layer(12c), a second shielding layer(13b) to prevent the gas(oxygen) and moisture from permeating into tube, a fourth adhesive layer(12d); and the outer surface layer(15) constituting the exterior of tube in order. The first and the second shielding layers(13a,13b) are selected from the group consisting of polyolefin and derivatives thereof, polyvinylidene chloride coating film, ethylene vinyl alcohol copolymer, nylon MXD6, aluminum deposited film, polyvinyl alcohol deposited film, ceramic deposited transparent film and aluminum oxide deposited transparent film. The laminate tube has an oxygen permeability of not more than 1 cc/m2·atm·24h at 20 deg.C and 85% RH and an moisture permeability of not more than 2 g/m2.24h at 38 deg.C and 90% RH.

Description

Laminated tube having plastic multi-layer film structure and method for preparing the same

The present invention relates to a laminate tube having a multilayer film structure composed only of a plastic material and a method for manufacturing the same. More specifically, the present invention relates to a plastic material having both gas and fragrance barrier properties and oxygen absorption function and a plastic material having excellent moisture barrier property. A laminate tube having a multilayer film structure in which the surface layer, the support layer, the adhesive layer, and the like are all formed using only a plastic material and each layer is formed, and the plastic film is dried without producing each layer of the tube by coextrusion. Or it relates to a method for producing a laminate tube produced by extrusion lamination.

In general, a laminate tube having a plastic multilayer film structure can be used as a tube for packaging various pasty materials, and especially for packaging toothpaste or ointment.

The early tube structure has long been used as a single layer of metal foil made of thick iron or the like. However, these metal tubes are expensive compared to other tube structures, are easy to enter, have little restoring force, are difficult to bend and are damaged by proper bending, and can also injure tube users when using the tubes. I had.

Recently, a laminate tube having a certain restoring force is generally used by using a thin aluminum layer as a barrier layer and stacking a plurality of polymers as a tube structure to compensate for these disadvantages. In addition, in recent years, a material composed of only a plastic film and having a barrier property similar to a tube in which an aluminum thin layer is applied as a barrier layer is also provided.

For example, Korean Patent Publication No. 1991-08844 discloses a multilayer flexible film structure in the form of a flexible tube commonly used for filling paste-type products, and the use of these film structures. According to the patent, a thin aluminum film layer is used as a barrier layer, and in addition, a plurality of polymer layers are bonded to each other, thereby providing a multilayer film structure having enhanced chemical resistance and enhanced strength and bending stability.

As described above, a laminate structure that is conventionally used is mainly an ethylene acrylic acid copolymer (EAA) having high adhesion to an inner thin film layer 3 as an intermediate layer 3 and having an inner side 2b and an outer side 2a as shown in FIG. 1. After application with the back and the like, the outermost surface layer 1 and the inner surface layer 4 are generally bonded to each other with a polyethylene film, and in some cases, a copolymer layer mixed with a pigment may be added.

In more detail, the aluminum thin plate was used as a blocking layer to suppress gas permeation and moisture permeation, and to bond polyethylene films to inner and outer layers to add chemical resistance, as well as to compensate to a certain extent that metals do not have resilience.

However, the laminated tube structure up to now has excellent gas and water barrier properties because it uses a thin aluminum plate as a barrier layer, but it is inconvenient to easily dent due to the deterioration of restoring force due to aluminum metal, and also bends when the tube is bent. There is a possibility that the cut part is broken or broken so that the contents can leak, the rigidity of the hard feeling due to the metal, and also may cause environmental pollution.

Accordingly, Korean Patent Application No. 2002-28590 discloses a surface layer composed of a tube inner surface layer forming an inner surface of a tube and a tube outer surface layer forming an outer surface, a gas barrier layer for preventing gas permeation into the tube, and a bonding between the surface layer and the gas barrier layer. A laminate tube structure comprising an adhesive layer, wherein the gas barrier layer is made of a plastic material selected from the group consisting of polyolefins and derivatives thereof, polyvinylidene chloride, ethylene vinyl alcohol copolymers and nylon MXD6. However, there is a need for a laminate tube that exhibits a higher level of gas barrier capability.

Therefore, in the present invention, as a result of intensive research to find a new material that can avoid the above-mentioned disadvantages while utilizing the advantages of the existing aluminum sheet, the aluminum sheet is a plastic material having excellent gas and fragrance barrier properties or excitation. By replacing the plastic material with the function of absorbing gas (oxygen) and the plastic material with excellent moisture barrier property, it is confirmed that the above-described problems of the existing tube can be solved while maximizing the advantages of the existing tube. It was completed.

Accordingly, an object of the present invention is to construct a laminated tube of a multi-layer film structure, by replacing the aluminum thin plate with a plastic material which has excellent gas and fragrance barrier properties and also has the function of oxygen absorption at the same time, gas and fragrance barrier properties and moisture barrier properties A plastic multilayer film that maintains similarity to laminate tubes and has excellent resilience that traditional laminate tubes do not have, making it convenient for consumers to use, providing bending stability, and relieving the rigidity of the tube to have a soft touch. An environmentally friendly laminate tube is provided.

Another object of the present invention is to provide a method for producing the laminate tube.

Laminate tube having a plastic multilayer film structure of the present invention for achieving the above object is a laminate tube having a plastic multilayer film structure, the first adhesive layer on the inner surface layer of the tube forming the inner surface of the tube, the gas (oxygen) into the tube And the first barrier layer, the second adhesive layer, the support layer, the third adhesive layer, which prevent the permeation of moisture, and the second barrier layer, the fourth adhesive layer, which prevents the permeation of gas (oxygen) into the tube, and the outer surface of the tube. The outer surface layer of the tube is sequentially laminated, the first and second barrier layer is a polyolefin and its derivatives, polyvinylidene chloride coating film, ethylene vinyl alcohol copolymer, nylon MXD6, aluminum deposition film, polyvinyl alcohol Selected from the group consisting of a deposited film, a ceramic deposited transparent film, and an aluminum oxide deposited transparent film, 1 cc / m at 20 ° C. and 85% RH. ^{It has} an oxygen permeability of ² · atm · 24hr or less and a moisture permeability of 2g / m ² · 24hr or less at 38 ° C. and 90% RH.

According to another aspect of the present invention, there is provided a method of manufacturing a laminate tube having a plastic multilayer film structure, in which a first adhesive layer on a tube inner surface layer forming an inner surface of a tube prevents penetration of gas (oxygen) and moisture into the tube. The first barrier layer, the second adhesive layer, the support layer, the third adhesive layer, the second barrier layer for preventing the permeation of gas (oxygen) and moisture into the tube, the fourth adhesive layer, and the tube outer surface layer forming the outer surface of the tube are sequentially stacked. Structure, which is laminated with a dry lamination method, an extrusion lamination method, or a combination thereof, wherein the first and second barrier layers are made of polyolefin and its derivatives, polyvinylidene chloride coating film, and ethylene vinyl alcohol copolymer. , Nylon MXD6, aluminum deposition film, polyvinyl alcohol deposition film, ceramic deposition transparent film, and aluminum oxide deposited transparent film Selected and is configured as having 2g / m ² · 24hr or less in moisture permeability of 20 ℃ and ^{85% RH 1cc / m 2 ·} atm · 24hr or less and the oxygen transmission rate of 38 ℃ and 90% RH in from.

1 is a cross-sectional view showing an example of a conventional laminate tube.

2 is a cross-sectional view showing one embodiment of a laminate tube according to the present invention.

Explanation of symbols on the main parts of the drawings

<Figure 1>

1: tube outer surface layer 2a and 2b: adhesive layer

3: intermediate layer (gas and odor barrier layer) 4: tube inner surface layer

<FIG. 2>

11: tube outer surface layer

12a: first adhesive layer 12b: second adhesive layer

12c: third adhesive layer 12d: fourth adhesive layer

13a: first barrier layer 13b: second barrier layer

14: intermediate support layer 15: tube inner surface layer

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

The laminate tube structure of the present invention is composed of a multilayer film structure in which a plurality of thermoplastic films having different physical properties are laminated by using a dry and / or extrusion lamination method.

According to a preferred embodiment of the present invention, the laminate tube structure of the present invention has a tube inner surface layer 11 forming an inner surface of the tube and an outer surface layer 15 of the tube forming an outer surface, as shown in FIG. And the support layer 14 between the second blocking layers 13a and 13b, the first blocking layer 13a and the second blocking layer 13b, which block gas, fragrance and moisture, and also add a function of oxygen absorption. It consists of the adhesive layers 12a, 12b, 12c, and 12d which adhere | attach each layer.

In the present invention, the tube preferably includes both the first blocking layer 13a and the second blocking layer 13b, but only one blocking layer may be formed if necessary. In addition, the first blocking layer 13a and the second blocking layer 13b may be the same as or different from each other. The total mass of the tube consists of at least 80% by weight of polyolefin and up to 20% by weight of the first and second gas barrier layers, excluding the adhesive layer.

As the material of the inner and outer surface layers 11 and 15 and the support layer 14 of the tube, polyolefin-based resins such as polyethylene having excellent chemical resistance and moisture barrier property may be used, and among them, particularly excellent in thermal adhesiveness. Polyethylene having excellent restoring force and soft touch is preferred. Particularly, among polyethylene, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), or copolymers thereof having excellent heat adhesion and chemical resistance are preferably used, and linear low density polyethylene having a bending strength of 110 kg / cm ² or less is most preferred. desirable.

The sealing strength is required to prevent the catching part from bursting due to any impact after heat bonding, and it is necessary to block moisture from the outside to prevent the deterioration of the contents. Especially in the case of the inner surface layer of the tube, the gas barrier layer is damaged by inhibiting chemical activity of the contents. This is because you have to use a material that doesn't work. And the thickness of the inner and outer surface layer (11 and 15) is preferably about 40 to 120㎛ that can have a suitable sealing strength and restoring force, the support layer 14 is formed to prevent the curling (curling) of the product As for the thickness, about 110-130 micrometers is preferable.

In addition, the tube inner surface layer 11 should not be added any other chemical components other than the polyolefin resin used as the surface layer material for the stability and hygiene of the contents. For example, antioxidants, ultraviolet stabilizers, slip agents, antistatic agents, and the like, which are added as necessary, are preferably added to the tube outer surface layer 15. In addition, an over-coating treatment or an anti-scratch agent may be added to the outermost layer to prevent scratching of the outer surface layer 15.

In addition, front printing (gold or black) for the purpose of blocking light may be applied to the outermost layer or the outer surface of the tube.

In the present invention, as the adhesive layers 12a, 12b, 12c and 12d of the tube, polyolefin-based materials such as polyurethane imparting adhesion can be used. Thus, the adhesive strength for bonding each component layer should be at least 500gf / 15mm. This means that it is not substantially peeled off by external stresses applied to the tube during use of the tube, including bending, folding and the like.

Specific to the laminate tube structure of the present invention, the barrier layer for blocking the gas permeated from the outside of the tube is a polyolefin and its derivatives, polyvinylidene chloride coating film, ethylene vinyl alcohol copolymer, nylon MXD6, aluminum deposition film, Polyvinyl alcohol vapor deposition film, ceramic vapor deposition transparent film, stick material can be used. The film is preferably polyethylene terephthalate (PET), nylon (Ny) or oriented polypropylene (OPP).

The gas barrier layers 13a and 13b have an oxygen permeability of 1 cc / m ² atm and 24hr or less at 20 ° C and 85% RH and a water permeability of 2g / m ² and 24hr or less at 38 ° C and 90% RH. desirable.

In addition, in the laminate tube structure of the present invention, the gas barrier layer may have a functional barrier layer having not only a gas barrier function but also an oxygen absorption function. Gas that is permeated from outside the tube may be blocked to some degree through the first and / or second barrier layers 13a and / or 13b, but there is some gas that is not blocked and permeated, and over time As the performance decreases little by little, the amount of gas permeated gradually increases, especially when the oxygen permeability increases. In addition, ethylene vinyl alcohol shows a great vulnerability to moisture, and when a lot of moisture is present, its barrier property tends to be greatly reduced.

Accordingly, the present invention includes a functional barrier layer having a gas blocking function and an oxygen absorbing function at the same time to absorb oxygen remaining in the tube and the contents as well as the gas that is permeated from the outside, thereby minimizing the damage caused by oxygen to preserve the contents. It was intended to greatly improve.

As the functional barrier layer, a thermoplastic resin containing an oxygen absorbent such as an iron-based composition, ascorbic acid, a polyhydric phenol compound, an organometallic compound, or a food additive system may be used. The oxygen permeability of the functional barrier layer is preferably 0.05 cc / m ² · atm · 24hr or less at 35 ° C. and 85% RH.

Although the thickness of the functional barrier layer depends on the amount of oxygen absorption required, the thickness of the functional barrier layer is preferably at least 10 to 30 μm. The reason is that when the thickness of the oxygen absorption layer is less than 8 μm, it is difficult to maintain the oxygen absorption performance for a long time. Because there is. In addition, the content of the oxygen absorbent contained in this layer is preferably about 10 to 50 wt%. The reason is that when the content of the oxygen absorbent is less than 10 wt%, the oxygen absorption performance may be lowered.

According to the present invention, each layer of the plastic multilayer film can be laminated by a dry lamination method, an extrusion lamination method, or a combination thereof. In addition, during the lamination process, the outermost layer is rolled into the inner surface and the outermost layer is rolled into the rolled state, thereby suppressing curling occurring in a general film, thereby easily inserting the machine into a round tube. It was.

The laminated tube according to the present invention configured as described above may be used as a tube for packaging various paste-like materials, and in particular, may be used for packaging toothpaste, ointment, and the like.

Hereinafter, the configuration and effects of the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the following examples.

Example 1

Using a dry laminator to prepare a plastic multilayer film having a layer structure of nine layers having a thickness (μm) and a material as follows by the lamination method.

2, A = 15, B = 12d, C = 13b, D = 12c, E = 14, F = 12b, G = 13a, H = 12a, and I = 15.

Structure: (Outer) A: B: C: D: E: F: G: H: I (Inner)

Thickness: 40: 3: 12: 3: 120: 3: 12: 3: 120 (unit: μm)

A: tube outer surface layer

Material: linear low density polyethylene

Melt Index: 2.7g / 10min

Flexural Strength: Below 110kg / cm ²

Heat Deflection Temperature: 107 ℃

Moisture ^{permeability: 2g / 30㎛ · m 2 ·} atm · 24hr

B, D, F and H: adhesive layer

Material: polyurethane resin

Adhesive Strength: 500g _f / 15mm or more

C: first gas barrier layer

Material: Aluminum Deposition PET

Gas permeability: 0.8cc / 20㎛m ² atm and 24hr or less (35 ℃, dry)

E: support layer

Material: linear low density polyethylene

Melt Index: 2.7g / 10min

Flexural Strength: Below 110kg / cm ²

Heat Deflection Temperature: 107 ℃

Moisture ^{permeability: 2g / 30㎛ · m 2 ·} atm · 24hr

G: second gas barrier layer

Material: Ethylene Vinyl Alcohol (EVOH)

Oxygen permeability: 1 cc / 20 μmm ² atm and 24hr or less (35 ° C, dry)

I: inner surface layer of the tube

Material: linear low density polyethylene

Melt Index: 2.7g / 10min

Flexural Strength: Below 110kg / cm ²

Heat Deflection Temperature: 107 ℃

Moisture ^{permeability: 2g / 30㎛ · m 2 ·} atm · 24hr

Example 2

In Example 1, the thickness of the first blocking layer was changed to 20 μm, except that the second gas blocking layer and the adhesive layer H were not laminated.

Structure: (Outer) A: B: C: D: E: F: I (Inner)

Thickness: 40: 3: 20: 3: 120: 3: 120 (unit: μm)

Example 3

The same procedure as in Example 1 was performed except that the functional barrier layer having a gas blocking function and an oxygen absorption function instead of the second gas barrier layer was replaced with a thickness of 20 μm.

Structure: (Outer) A: B: C: D: E: F: S: H: I (Inner)

Thickness: 40: 3: 12: 3: 120: 3: 20: 3: 120 (unit: μm)

S: functional barrier layer

Material: ethylene vinyl alcohol (EVOH) + ascorbic acid (oxygen absorber)

Moisture permeability: 0.5cc / 20㎛m ² atm and 24hr or less (35 ℃, 85% RH)

Comparative Example 1

A plastic multilayer film having a seven-layered layer structure having the thickness and material as described below was manufactured by coextrusion using five extruders.

(Inside) A: B: C: D: E: F: G (outside) = 66: 76: 17: 22: 17: 76: 66

A: tube outer inner surface layer

Material: linear low density polyethylene

Melt index: 2.7g / 10min

Flexural Strength: 110 kg / ㎠

Heat Deflection Temperature: 107 ℃

Moisture Permeability: 2 g / 30 ㎛ ?? ㎡ ?? atm ?? 24hr

B: inner surface layer inside the tube

Material: linear low density polyethylene (85 wt%)

Melt index: 2.7g / 10min

Flexural Strength: 110 kg / ㎠

Heat Deflection Temperature: 107 ℃

Moisture Permeability: 2 g / 30 ㎛ ?? ㎡ ?? atm ?? 24hr

Antimicrobial and Masterbatch White (15 wt%)

C, E: adhesive layer

Material: linear low density polyethylene

Adhesive Strength: Non-peelable (not torn)

D: gas barrier layer

Material: Ethylene Vinyl Alcohol (EVOH)

Oxygen permeability: 0.5㏄ / 20㎛ ?? ㎡ ?? atm ?? 24hr (35 ℃, dry)

E: tube inner outer surface layer

Material: linear low density polyethylene (85 wt%)

Melt index: 2.7g / 10min

Flexural Strength: 110 kg / ㎠

Heat Deflection Temperature: 107 ℃

Moisture Permeability: 2 g / 30 ㎛ ?? ㎡ ?? atm ?? 24hr

Antimicrobial and Masterbatch White (15 wt%)

G: tube outer outer surface layer

Material: linear low density polyethylene (85 wt%)

Melt index: 2.7g / 10min

Flexural Strength: 110 kg / ㎠

Heat Deflection Temperature: 107 ℃

Moisture Permeability: 2 g / 30 ㎛ ?? ㎡ ?? atm ?? 24hr

Antimicrobial and Masterbatch White (15 wt%)

As a result of measuring the gas barrier property, the moisture barrier property and the restoring force (bending stability) of the plastic films of Examples 1 to 3 and Comparative Example 1, it was confirmed that the plastic films of Examples 1 to 3 were excellent in all of the above items. I could confirm it.

As described above, the laminated tube of the plastic multilayer film of the present invention is a plastic material having excellent gas barrier properties or a plastic material having both gas and fragrance barrier properties and oxygen absorption at the same time, instead of using aluminum foil as a gas barrier layer. Gas and fragrance barrier properties and moisture barrier properties are maintained at the same level as those of conventional laminate tubes, while having excellent resilience that conventional tubes do not have, resulting in bending stability and convenience for consumers. It is possible to manufacture a high quality environmentally friendly laminate tube having a soft touch by eliminating the rigidity due to the aluminum sheet.

Claims (11)

A laminate tube having a plastic multilayer film structure, The first adhesive layer 12a, the first barrier layer 13a, the second adhesive layer 12b, and the support layer, which prevent permeation of gas (oxygen) and moisture into the tube on the inner surface layer 11 forming the inner surface of the tube. 14, the third adhesive layer 12c, the second barrier layer 13b for preventing the permeation of gas (oxygen) and moisture into the tube, the fourth adhesive layer 12d and the tube outer surface layer 15 forming the outer surface of the tube. ) Is sequentially laminated, the first and second barrier layers (13a and 13b) is a polyolefin and its derivatives, polyvinylidene chloride coating film, ethylene vinyl alcohol copolymer, nylon MXD6, aluminum deposition film, Selected from the group consisting of polyvinyl alcohol vapor deposition film, ceramic vapor deposition transparent film, and aluminum oxide vapor deposition transparent film, oxygen permeability up to 1cc / m ² atm and 24hr at 20 ° C and 85% RH and 38 ° C and 90% RH from 2g / m ² ·, it characterized in that it has a moisture permeability of less than 24hr Laminated plastic tube having a multi-layer film structure. The laminate tube of claim 1, wherein only one blocking layer of the first and second blocking layers is formed. The laminate tube according to claim 1 or 2, wherein the mass ratio of the blocking layer in the remaining layers other than the adhesive layer in the tube is at most 20 wt%. 3. The laminate tube of claim 1 or 2, wherein said barrier layer further comprises an oxygen absorbent selected from the group consisting of iron-based compositions, polyhydric phenol compounds, ascorbic acid, organometallic compounds, and food additives. The laminate tube of claim 4, wherein the barrier layer has a gas permeability of 0.05 cc / m ² · atm · 24hr or less at 35 ° C. and 85% RH. The laminate tube according to claim 1, wherein the surface layers (11 and 15) and the support layer (14) inside and outside the tube are made of polyolefin resin. The laminate tube according to claim 6, wherein the polyolefin resin is a linear low density polyethylene having a bending strength of 110 kg / cm ² or less. The laminate tube of claim 1, wherein the film is polyethylene terephthalate (PET), nylon (Ny), or oriented polypropylene (OPP). The laminate tube according to claim 1, wherein the tube outer surface layer (15) further comprises an over-coating treatment or additive for preventing scratches. The laminate tube according to claim 1, wherein the adhesive strength of the adhesive layer is 500 gf / 15 mm or more. A method for producing a laminate tube, characterized in that each layer of the tube having the laminated structure according to claim 1 or 2 is laminated by a dry lamination method, an extrusion lamination method, or a combination thereof.