KR100801860B1 - High barrier multilayer film for medical solution - Google Patents

Abstract

A high-impermeability multilayer film for functional fluid is provided to secure good transparency, heat resistance, and sealability, and durability by making an inner layer of a non-oriented film and intermediate and outer layers of a biaxially oriented film. A high-impermeability multilayer film for functional fluid is composed of a first blocking layer(1) made of a PET(Polyethylene Terephthalate) film deposited with metal oxides; a second adhesive layer(2) made of ester polyurethane polymer; a third intermediate layer(3) made of a polyamide polymer film; a fourth adhesive layer(4) made of ester polyurethane polymer; and a fifth layer(5) made of a PP(Polypropylene) film. Metal oxide is produced by vacuum-depositing silicon oxide. The adhesive layer is formed through a solvent-free two-liquid type adhesive agent.

Description

High Barrier Multilayer Film for Functional Solution

1 is a schematic cross-sectional view of a five-layer film according to the present invention.

* Explanation of symbols for main parts of the drawings

1: first layer 2: second layer

3: third layer 4: fourth layer 5: fifth layer

The present invention relates to a high barrier multilayer film for functional fluids, and more particularly, a first layer which is a barrier layer made of polyethylene terephthalate deposited with a metal oxide; A second layer of an adhesive layer made of an ester polyurethane polymer, a third layer of an intermediate layer made of a polyamide polymer, a fourth layer of an adhesive layer made of an ester polyurethane polymer, a polypropylene homopolymer, and a polypropylene copolymer It relates to a high barrier multilayer film for functional fluids composed of a fifth layer made of a polypropylene polymer.

Plastic bags for packaging chemical liquids require properties such as flexibility, transparency, gas barrier properties, pharmaceutical compatibility, sterilization heat resistance, heat sealability and drop impact resistance. The present invention provides a bag-type high-breaking flexible plastic container having a plurality of (two or more) rooms, that is, an inner bag containing a functional sap, and a wrapper to protect and protect the inner bag. The present invention relates to a plastic film that can be used for an outer bag in a flexible container system for functional fluids composed of an outer bag. The barrier property is evaluated as a barrier against the surface leakage of the functional fluid within the expiration date, and is generally evaluated as a barrier against oxygen and water vapor.

The bag-type, high-breaking flexible plastic container with a plurality of (more than two) mentioned above stores each functional sap component that is likely to react with each other for long-term storage in a well-sealed state in a large number of bags. Press the room by hand to easily open the diaphragm in each room, shake the bag well, and mix the ingredients to take the functional fluid mixture from the spike port with a syringe (a set of fluid), which is hygienic and safe. By doing so, it will function.

The development of high-permeability flexible containers for functional fluids consisting of inner and outer bags with multiple rooms has been studied around Europe for about 10 years, and researches to compensate for not only barrier properties but also drop impact resistance are being accelerated. Inner bag requires oxygen and moisture barrier, sterilization heat resistance, transparency, drop impact resistance, flexibility, etc. Outer bag requires oxygen and moisture barrier, sterilization heat resistance and transparency, but drop impact resistance and flexibility are not so important. Rather, an appropriate modulus of elasticity is required for the vacuum forming process. In addition, since the outer bag is usually subjected to vacuum forming process, it must be stretched and heat-bonded by heat, maintains a constant thickness even after stretching, and has no change in barrier property, and is durable even after vacuum molding. A technique is required that must be maintained. Germany's Pactiv Co., Ltd., which is evaluated as the best quality as an outer bag, has an outer layer (polypropylene) / adhesive layer (polyolefin adhesive) / oxygen barrier intermediate layer (ethylene vinyl alcohol polymer) / adhesive layer (polyolefin adhesive) / heat seal It is a coextrusion film which has a multilayer (5-layer) cross-sectional structure of an inner layer (polypropylene). However, Pactiv's product has a cloudiness of 50% or more after sterilization (121 ℃, 30 minutes), which is quite cloudy even with the naked eye, which makes it difficult to observe and check the contents of foreign substances in the bag. There is a need for improvement.

Functional sap bags are required to have excellent gas barrier properties, drop impact resistance and transparency compared to conventional sap bags. In particular, in the case of the outer bag, a high transparency film capable of confirming whether foreign matters are mixed in the functional sap is required. Due to its characteristics, a film manufacturing technology capable of securing transparency after sterilization at a high temperature of 121 ° C. is required. In addition, since various nutrient sap that can react with oxygen is filled in the bag, high oxygen barrier property is required.

The present invention is to solve the above problems, the inner layer is composed of a non-stretch film using a polypropylene homopolymer or copolymer, the thickness is formed of 40 ~ 120㎛, the middle layer is a polyamide polymer (nylon 6) It consists of used biaxially oriented film, 10 ~ 25㎛, the outer layer is composed of polyethylene terephthalate biaxially oriented film deposited metal oxide, and developed a medical multilayer film formed of 5 ~ 20㎛ thickness of the sap, It is an object of the present invention to develop a medical multilayer film suitable for outer packaging of a pouch-type bag containing a medical solution such as blood and having excellent transparency, heat resistance, sealing property, durability and cost competitiveness.

The present invention provides a film that can be used for an outer bag in a bag for storing and using a functional sap consisting of two inner bags and an outer bag; A second layer of an adhesive layer made of an ester polyurethane polymer, a third layer of an intermediate layer made of a polyamide polymer, a fourth layer of an adhesive layer made of an ester polyurethane polymer, a polypropylene homopolymer, and a polypropylene copolymer It relates to a high barrier multilayer film for functional fluids, characterized in that consisting of a fifth layer made of a polypropylene polymer.

In the high-permeability multilayer film for functional transfusion of the present invention, the barrier layer is manufactured using a polyethylene terephthalate (PET) film on which metal oxide is deposited, and silicon oxide is used as the metal oxide deposited on the film. In addition, the high-layered multilayer film for functional transfusion of the present invention is characterized in that the intermediate layer is made of a polyamide polymer. In addition, in the high-performance multilayer film for functional sap of the present invention, the inner layer is characterized in that the polypropylene polymer selected from polypropylene homopolymer and polypropylene copolymer. In addition, in the high-permeability multilayer film for functional transfusion of the present invention, the adhesive layer is characterized in that the ester-based polyurethane polymer. In addition, in the high translucent multilayer film for the functional sap of the present invention, the film layer is characterized in that the laminate is manufactured together in a clean room conditions.

The present invention is a film that can be used for an outer bag in a bag for storing and using a functional sap consisting of two inner bags and an outer bag, the first layer (1) being a barrier layer made of polyethylene terephthalate deposited with a metal oxide, and an ester-based poly A second layer 2 of an adhesive layer made of a urethane polymer, a third layer 3 of an intermediate layer made of a polyamide polymer, a fourth layer 4 of an adhesive layer made of an ester-based polyurethane polymer, a polypropylene homopolymer, and A multilayer film comprising a fifth layer (5) made of a polypropylene polymer selected from polypropylene copolymers, and the barrier layer is an outer layer.

In the present invention, the outer layer is a layer imparting a function of blocking oxygen, and is manufactured using polyethylene terephthalate deposited with a metal oxide. Silicon oxide is used as the silicon oxide, and silicon oxide is composed of silicon monoxide (SiO), which is a brown solid, and silicon dioxide (SiO ₂ , silica), which is a colorless solid. Silicon oxide deposition film is heat-deposited silicon oxide with high energy electron beam, and the barrier property of SiOx becomes worse when the amount of oxygen (O) containing is large. Therefore, the oxygen atmosphere of SiO vapor is adjusted by adjusting the atmosphere of oxygen during deposition process. (O) is deposited on the base material film with a composition in the range of 1.5 to 1.8. Gas barrier property is SiO _1.5 indicate a significantly improved performance over SiO _{1 .8,} opposed to the color of the deposited film is SiO _{1 .5} takes on a brown under the influence of silicon monoxide. In general, the thickness of the deposited layer is preferably 40 to 200 nm. If the thickness is less than 40 nm, it is difficult to uniformly deposit the gas barrier property, and if the thickness is too thick at 200 nm or more, the durability of the entire film, such as the possibility of cracking, may be reduced. The thickness of the PET film is generally preferably 10 to 25 μm.

In the present invention, the intermediate layer uses a biaxially oriented film made of polyamide as a layer to impart stiffness and heat resistance to the entire film, and the polyamide is made of polyamide 6 or polyamide MXD (meta xylenediamine and adipic acid polymer). In general, the thickness is preferably 10 to 25 µm.

In the present invention, the inner layer is a layer for imparting properties such as heat sealing property to the film, and uses a non-stretched film using a polypropylene homopolymer or copolymer, and the thickness is preferably 40 to 120 μm. If the thickness is less than 40㎛ the thickness of the entire film is too thin, the strength is difficult to come out properly, and if the thickness is more than 120㎛ less flexibility of the film.

In the present invention, an intermediate layer for imparting adhesion between the layers to adhere to each other to make the polyethylene terephthalate film used for the outer layer, the polyamide film used for the intermediate layer and the polypropylene film used for the inner layer into one product is provided. Present and ester-based polyurethane resins are used. The thickness of the adhesive layer is preferably 1 ~ 10㎛, in this case, the coating amount of the adhesive is 1 ~ 10g / m2, in the case of less than 1g / m2 it is difficult to uniformly apply the adhesive, resulting in peeling, uneven physical properties, etc. 10g If more than / m 2 is caused by problems such as the transparency is reduced and the production cost is increased by applying more than the adhesive.

In addition, the multilayer film of the present invention is produced by a known method such as water-cooled or air-cooled coextruded tubular inflation method, coextruded T-die method, lamination method. In particular, each layer can maintain a certain thickness, and a lamination method that can ensure high transparency is suitable.The lamination method includes wet lamination method, dry lamination method, solvent-free lamination method, wax lamination method, thermal lamination method, extrusion coating lamination method, and the like. Although there are the same kinds, dry lamination and solvent-free lamination are suitable for producing medical films.

In the solventless laminating method, the laminating process consists of supplying the first feed (unwinding), applying a solvent-free adhesive, supplying the second feed (unwinding), laminating, winding the product, curing, and slitting, and the final film has three or more layers. In the composition, after winding the product of two layers, the adhesive is cured to a certain degree, and then the film of the first layer is worked in the same process as above and finally cured. The working speed, ie, the speed at which the film is laminated, depends on the type of film and the mechanical condition, but is preferably 30 to 200 m per minute. If the film feed speed is too slow, it is difficult to control the tension, which may result in a decrease in physical properties, and the production efficiency may be too low. If the film is too fast, it may be difficult to control the tension and apply an appropriate amount of adhesive.

The adhesive is a polyurethane polymer (a high molecular material having a urethane bond (-NHCO)) is a two-component adhesive formed by the reaction between an isocyanate (-NCO) functional group and a hydroxy (-OH) functional group. When these are mixed in a suitable blending ratio and applied to the film, the film can be adhered (by lamination). Both the main body and the curing agent are 100% solids, so they are in a liquid state but have a very high viscosity at room temperature. Therefore, it is important to heat to an appropriate temperature 2-3 hours before use. If the temperature is too high, the curing time or use time of the adhesive may be shortened. If the temperature is too low, the adhesive may not be properly discharged and may not be mixed at a predetermined compounding ratio. Each roll to which the adhesive is supplied and transported must also be preheated before use at an appropriate temperature to maintain the viscosity of the adhesive. Too high a temperature may shorten the curing time of the adhesive, which may interfere with the operation, and when the temperature is too low, the viscosity may be high and may not be properly applied to the film.

The adhesive should be applied by mixing the main agent and the hardener in the prescribed proportions. The blending ratio should be mixed in the proportion of 30 to 50 of the curing agent in the main 100 by weight. When the ratio of the curing agent is low, the curing is not performed properly, and the physical properties are lowered. When the ratio is high, the uncured reactant remains, which also brings about a decrease in physical properties.

In the case of the dry lamination method, the process is the same as the solvent-free method, but a drying process for drying the solvent after the application of the adhesive is added. The adhesive is dissolved in an organic solvent and applied to a film. The solvent of the adhesive applied by hot air is evaporated to dryness and then bonded to another film to obtain a product. The adhesive used here is one-component reaction type and two-component reaction type. The one-component type uses a polyurethane prepolymer having an isocyanate functional group at the end of the polymer and reacts with moisture in the air or moisture adsorbed on the film surface to form a urea bond to cure. The two-component type consists of two liquids of a main agent having a hydroxy functional group and a hardener having an isocyanate functional group at the end of the polymer, and the urethane bond is formed by the reaction of the two functional groups to cure.

Compared to existing Pactiv products (polypropylene / ethylene vinyl alcohol copolymer / polypropylene coextruded film), the developed product (silicon oxide deposited polyethylene terephthalate / nylon / polypropylene lamination film) Although the overall physical properties are similar, the strength and post-sterilization haze (Haze) is excellent, especially Haze (Haze) was shown to be significantly improved compared to the existing product in terms of transparency, which is an important requirement characteristic of the sap bag, it is shown in Table 1.

Table 1 Property Comparison Table

Item unit Pactiv Products Invention Product The tensile strength kg / cm ² 410 777 Tensile Modulus kg / cm ² 13,542 14,231 Haze after sterilization % 60.0 12.6 Oxygen Permeability cc / m ² ㆍ day · atm 3.0 ↓ 3.0 ↓

The present invention has been described through the following examples.

Example 1

According to a preferred embodiment of the present invention, a five layered film as shown in Fig. 1 was prepared by a solventless lamination method. The outer layer is composed of a polyethylene terephthalate film having a thickness of 12 μm, and silicon oxide, which is a metal oxide, is deposited on one side of the film. The middle layer is composed of a polyamide film having a thickness of 15 μm, and both sides of the film are corona discharged to improve adhesion. The inner layer consists of a film made of propylene polymer and has a thickness of 80 μm. The adhesive layer for adhering each film is composed of an ester-based polyurethane polymer and has a thickness of 2 μm. The adhesive is a solvent-free two-component type consisting of a main agent and a curing agent, which must be supplied by mixing the two components well before use. The preheating temperature of the main material of the adhesive and the curing agent storage tank is 60 ℃, the temperature of the adhesive transfer line and the connection part is 60 ℃, the temperature of each feeding roll is 60 ℃, and the laminating roll temperature is 65 ℃. To work. The adhesive blending ratio is mixed by weight ratio of the curing agent 40 to the main 100. The laminated film is left to stand at 45 ° C. for about 3 days to cure the adhesive. The prepared film was tested for tensile strength, modulus, cloudiness after sterilization test, oxygen permeability, and the like.

Example 2

The inner layer was carried out in the same manner as in Example 1 except that 10 parts by weight of the propylene block copolymer was mixed with the propylene polymer.

Example 3

It carried out by the method similar to Example 1 except using a solvent type two-component adhesive for an adhesive layer. In the case of the solvent type, preheating of the adhesive is not necessary. Instead, the work is performed after drying the solvent at 80 ° C. after the application of the adhesive.

Table 2 Property Evaluation Results of Examples

Item unit Example 1 Example 2 Example 3 The tensile strength kg / cm ² 700 704 730 Tensile Modulus kg / cm ² 14,564 14,234 14,963 Haze after sterilization % 13.7 24.3 15.4 Oxygen Permeability cc / m ² ㆍ day · atm 3.0 ↓  3.0 ↓ 3.0 ↓

The inner layer of the present invention is composed of a non-stretched film using a polypropylene homopolymer or copolymer, the thickness is formed of 40 ~ 120㎛, the middle layer is composed of a biaxially stretched film using a polyamide polymer (nylon 6), It is formed of 10 ~ 25㎛, the outer layer is composed of polyethylene terephthalate biaxially oriented film deposited metal oxide and the medical multilayer film formed of 5 ~ 20㎛ thickness is a pouch (pouch) containing a medical solution such as sap, blood It is suitable for outer packaging of bag, and it is expected to be useful for medical industry because of its transparency, heat resistance, sealing property, durability and cost competitiveness.

Claims (5)

A first layer which is a barrier layer made of a polyethylene terephthalate film deposited with a metal oxide; A second layer, which is an adhesive layer made of an ester-based polyurethane polymer; A third layer, which is an intermediate layer made of a polyamide polymer film; A fourth layer, which is an adhesive layer made of an ester polyurethane polymer; A high barrier multilayer film for functional fluids, comprising a fifth layer made of a polypropylene film According to claim 1, wherein the metal oxide is silicon oxide high-definition barrier multifunctional film, characterized in that the vacuum deposition The method of claim 1, wherein the adhesive layer is a high-performance multilayer film for functional fluids, characterized in that using a solvent-free two-component adhesive. The method of claim 1, wherein the adhesive layer is a high-performance multilayer film for functional fluids, characterized in that using a solvent two-component adhesive. According to claim 1, wherein the film layer is a high-permeability multilayer film for functional fluids, characterized in that the laminate is manufactured in a clean room conditions

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